Lithium-selective ion exchange materials compositions and manufacturing methods thereof

Abstract

The present disclosure relates to composition of lithium-selective ion exchange materials and methods for the production of the same. Disclosed herein are compositions of lithium-selective ion exchange materials that exhibit optimal textural properties for advantageous exchange of lithium and hydrogen ions, while also exhibiting optimal hydrodynamic properties to pressure drop through a packed bed and settling velocity - that makes the incorporation of said compositions into industrial lithium extraction equipment advantageous.

Description

[0001] Attorney Docket No.: 733PCT601

[0002] LITHIUM-SELECTIVE ION EXCHANGE MATERIALS COMPOSITIONS AND MANUFACTURING METHODS THEREOF

[0003] CROSS REFERENCE TO RELATED APPLICATION

[0004]

[0001] This application claims priority under Article 8 of the Patent Cooperation Treaty (PCT) to U. S. Provisional Patent Application No. 63 / 779,138, filed March 27, 2025, entitled “LITHIUM-SELECTIVE ION EXCHANGE MATERIALS COMPOSITIONS AND MANUFACTURING METHODS THEREOF,’’ the entire contents of which are fully incorporated herein by reference as if fully set forth below.

[0005] BACKGROUND OF THE INVENTION

[0006]

[0002] Lithium is an essential element for high-energy rechargeable batteries and other technologies. Lithium can be found in a variety of liquid solutions, including natural and synthetic brines and leachate solutions from minerals and recycled products.

[0007] SUMMARY OF THE INVENTION

[0008]

[0003] In one aspect, disclosed herein is a lithium-selective ion exchange material composition, said composition comprising:

[0009] a) particles of a mixed metal oxide,

[0010] i) wherein said mixed metal oxide comprises lithium, oxygen, and a transition metal, ii) wherein the transition metal is selected from titanium and manganese, and iii) wherein the molar ratio of lithium to transition metal is from 0.25: 1 to 4: 1;

[0011] b) one or more optional matrix materials,

[0012] i) wherein the particles of a mixed metal oxide are coated by, embedded in, adhered to, or otherwise supported by the one or more matrix materials;

[0013] c) wherein the lithium-selective ion exchange material composition is in the form of particles, wherein the particles exhibit the following properties:

[0014] i) a specific pore volume of 0.01 ml / g to 0.25 ml / g, as determined by N2 physisorption, ii) a specific surface area of 1 m2 / g to 100 m2 / g, as determined by the Brunauer-Emmett- Teller (BET) method using N2 physisorption data,

[0015] iii) a dlO larger than 1 pm, and

[0016] iv) a d90 smaller than 1 mm.

[0017]

[0004] In another aspect, disclosed herein is a process for manufacturing a lithium-selective ion exchange material composition, the process comprising:Attorney Docket No.: 733PCT601

[0018] (a) generating the mixed metal oxide, wherein the mixed metal oxide is generated by:

[0019] (i) contacting a lithium salt precursor with a metal precursor to generate a synthesis mixture, and

[0020] (ii) heating said synthesis mixture to form the mixed metal oxide;

[0021] (b) optionally embedding the mixed metal oxide in a matrix material

[0022] (c) selectively sizing the mixed metal oxide, the metal precursor, the lithium salt precursor, the matrix material, the lithium-selective ion exchange material composition, or any combination thereof;

[0023] wherein the lithium-selective ion exchange material composition is in the form of particles exhibiting the following properties:

[0024] 1) the pore volume is from 0.001 ml / g to 0.1 ml / g;

[0025] 2) the specific surface area is from 1 m2 / g to 100 m2 / g;

[0026] 3) the particle size of 99% of the composition is from about 5 to 500 pm.

[0027]

[0005] In another aspect, disclosed herein is a method of extracting lithium from a liquid resource through the reversible exchange of hydrogen and lithium, the method comprising: i) treating any one of the lithium-selective ion exchange material compositions disclosed herein with an acid to release lithium and yield a protonated lithiumselective ion exchange material,

[0028] ii) performing lithium extraction cycles, wherein each cycle comprises

[0029] (1) contacting the protonated lithium-selective ion exchange material to a liquid resource to absorb lithium therefrom and yield a lithium-enriched lithiumselective ion exchange material;

[0030] (2) treating the lithium-enriched lithium-selective ion exchange material with an acid eluent solution to yield a synthetic lithium solution and regenerate the protonated lithium-selective ion exchange material.

[0031]

[0006] In another aspect, disclosed herein is a method of extracting lithium from a liquid resource with recycled lithium-selective ion exchange material, the method comprising:

[0032] iii) treating a any one of the recycled lithium-selective ion exchange material compositions disclosed herein with an acid to release lithium and yield a recycled protonated lithium-selective ion exchange material,

[0033] iv) performing lithium extraction cycles, wherein each cycle comprises

[0034] (1) contacting the recycled protonated lithium-selective ion exchange material to a liquid resource to absorb lithium therefrom and yield a recycled lithium-enriched lithium-selective ion exchange material;Attorney Docket No.: 733PCT601

[0035] (2) treating the recycled lithium-enriched lithium-selective ion exchange material with an acid eluent solution to yield a synthetic lithium solution and regenerate the recycled protonated lithium-selective ion exchange material.

[0036] INCORPORATION BY REFERENCE

[0037]

[0007] All publications, patents, and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference.

[0038] BRIEF DESCRIPTION OF THE DRAWINGS

[0039]

[0008] The novel features of the disclosure are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present disclosure will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the disclosure are utilized, and the accompanying Tables and Figures (also “Figure” and “FIG.” herein), of which:

[0040]

[0009] FIG. 1 provides an example nitrogen physisorption isotherm of one of an exemplary composition, according to embodiments of the disclosure.

[0041]

[0010] FIG 2. provides an example pore size distribution of one of an exemplary composition, according to embodiments of the disclosure.

[0042] [Oil] FIG 3. provides an example particle size distribution of one of an exemplary composition, according to embodiments of the disclosure.

[0043]

[0012] FIG.4 provides a flowchart of an example method for manufacturing a lithium-selective ion exchange material composition, according to embodiments of the disclosure.

[0044]

[0013] FIG.5 provides a flowchart of an example method for extracting lithium from a liquid resource, according to embodiments of the disclosure.

[0045]

[0014] FIG.6A provides example lithium recovery rates across lithium extraction cycles based on the use of compositions including bound fines, according to embodiments of the disclosure.

[0046]

[0015] FIG.6B provides example eluate molar purities across lithium extraction cycles based on the use of compositions including bound fines, according to embodiments of the disclosure.

[0047] DETAILED DESCRIPTION OF THE INVENTIONAttorney Docket No.: 733PCT601

[0048]

[0016] Lithium can be extracted from liquid resources using an ion exchange process based on inorganic ion exchange materials. Inorganic ion exchange materials can absorb lithium ions from a liquid resource while releasing hydrogen ions, and subsequently exchange the absorbed lithium ions for hydrogen ions in the presence of excess acid. The ion exchange process can be repeated to extract lithium ions from a liquid resource and yield a synthetic lithium solution, or eluate. The synthetic lithium solution contains a higher purity and concentration of lithium relative to the liquid resources, and can be further processed into chemicals for the battery industry or other industries. Lithium products include high value salts such as lithium carbonate, lithium hydroxide, and other lithium chemicals.

[0049]

[0017] A major challenge for lithium extraction using lithium-selective ion exchange materials is achieving material compositions with properties that result in the optimal extraction process for lithium. Optimal extraction processing includes, but is not limited to, achieving a high recovery rate of the lithium, maintaining a high lithium product purity, and minimizing degradation of the ion exchange material when extracting lithium form a variety of liquid resources. Such compositions must efficiently exchange lithium and hydrogen ions from solutions to the solid crystalline matrix of the ion exchange materials. It is therefore advantageous to prepare materials compositions with optimal physicochemical, textural, and hydrodynamic properties to facilitate interaction between the solutions and the solid ion exchange media. In some embodiments, said properties maximize the surface -to-volume ratio of the ion exchange material, thus facilitating exchange. Preferred embodiments exhibit certain specific surface areas, pore volumes, and particle size distributions that maximize exchange of lithium and hydrogen ions, while allowing flow of fluids to and from said particles.

[0050]

[0018] Optimal extraction processing also includes incorporation of the lithium-selective ion exchange material into systems for commercial lithium extraction. Such systems and processes often require flowing liquids, including liquid resources and acids, over packed beds or fluidized beds of ion exchange materials. Such systems and processes often require specific hydrodynamic properties that make said ion-exchange materials amenable to transport and conveyance through systems for lithium extraction.

[0051]

[0019] Disclosed herein are compositions of lithium-selective ion exchange materials that exhibit optimal textural properties - including but not limited to specific surface areas, pore volumes, and particle size distributions - for advantageous exchange of lithium and hydrogen ions, while also exhibiting optimal hydrodynamic properties - including, but not limited to, pressure drop through a packed bed and settling velocity - that makes the incorporation of said compositions into industrial lithium extraction equipment advantageous.Attorney Docket No.: 733PCT601

[0052]

[0020] A further aspect of said lithium-selective ion exchange material compositions is manufacturing said lithium-selective ion exchange material in a manner that results in advantageous properties for optimal lithium extraction processing. Said manufacturing processes and systems can be advantageously designed to manufacture said materials in a manner that is economical, efficient, and environmentally friendly.

[0053]

[0021] There is a need therefore for compositions of lithium-selective ion exchange materials with optimal properties for processing of liquid resources for lithium extraction. Herein, compositions of lithium-selective ion exchange materials, and systems, methods, and processes for their manufacture are disclosed. Said compositions result in optimal physicochemical, textural, and hydrodynamic properties of said lithium-selective ion exchange materials, which result in their efficient use in commercial lithium extraction systems.

[0054]

[0022] In specific aspects described herein, said composition comprise a particles of a mixed metal oxide with specific textural properties. In specific aspects described herein, said composition comprise a particles of a mixed metal oxide and a matrix material, with specific textural properties. In a further aspect, said compositions exhibit specific hydrodynamic properties. In a further aspect, said lithium-selective ion exchange material is used to extract lithium from a liquid resource to produce a purified synthetic lithium solution. In a further aspect, said lithium extraction occurs within devices design for efficient utilization of said ion exchange material for lithium extraction.

[0055]

[0023] In an aspect, disclosed herein are compositions of a lithium-selective ion exchange material comprising particles of a mixed metal oxide. In some embodiments, said compositions exhibit specific physicochemical, textural, and hydrodynamic properties which include: a molar ratio of lithium to a transition metal, specific pore volume, specific surface area, particle size distributions (including d5, dlO, d90, d95, and -400M%), pressure drops, and settling velocities. In some embodiments, the compositions of lithium-selective ion exchange material comprise particles of a mixed metal oxide and one or more matrix material(s), wherein said compositions exhibit specific textural and physicochemical properties. In some embodiments, said physicochemical, textural, and hydrodynamic properties result from the manufacturing process used for production of the lithium-selective ion exchange material. In some embodiments, said physicochemical, textural, and hydrodynamic properties result from the physicochemical, textural, and hydrodynamic properties of mixed metal oxide and / or matrix material used to manufacture the lithium-selective ion exchange material. In some embodiments, said physicochemical, textural, and hydrodynamic properties (“properties”) result from the properties of mixed metal oxide used to manufacture the lithium-selective ion exchange material, and theAttorney Docket No.: 733PCT601

[0056] properties of mixed metal oxide themselves depend on the properties of the metal precursor and / or lithium salt precursor used to manufacture the mixed metal oxide. As such, the properties of the lithium-selective ion exchange material compositions disclosed herein are a result of the metal precursor, lithium salt precursor, matrix material, and / or mixed metal oxide used to manufacture said material.

[0057]

[0024] In an aspect, the properties of the metal precursor, lithium salt precursor, matrix material, and / or mixed metal oxide are controlled to yield optimal properties of the lithium-selective ion exchange material. In a related aspect, the properties of the lithium-selective ion exchange material are controlled by (and depend on) the properties of the metal precursor, lithium salt precursor, matrix material, and / or mixed metal oxide they are manufactured from. In a further aspect, the properties of the mixed metal oxide are controlled to yield optimal properties of the lithium-selective ion exchange material. For example, the use of mixed metal oxide with high specific surface areas yields a lithium-selective ion exchange material with a high specific surface area, as exemplified in exemplary compositions 5 and derived composition 15. In yet another example, the use of mixed metal oxide with high specific pore volume yields a lithiumselective ion exchange material with a high specific pore volume, as exemplified in exemplary compositions 5 and derived composition 15.

[0058]

[0025] In one aspect, the lithium-selective ion exchange material comprises particles of the mixed metal oxide on their own (i.e. without an optional matrix material). In some embodiments, the mixed metal oxide comprises lithium and a transition metal, wherein said transition metal is selected from titanium or manganese. Thus, the properties of the lithium-ion exchange material correspond to those of the mixed metal oxide. In some embodiments, the mixed metal oxide exhibits a controlled particle size distribution, as in exemplary compositions 4 to 8 in table 1; thus, the lithium-selective ion exchange material composition resulting in using said mixed metal oxide as an ion exchange material exhibit these controlled and advantageous particle size distributions. In these embodiments, said advantageous particle size distribution lead to advantageous properties, including but not limited to the high specific surface area, high pore volume, low pressure drop and fast settling velocity.

[0059]

[0026] In an aspect, the properties of the metal precursor or lithium salt are controlled to yield optimal properties of the mixed metal oxide. In a related aspect, the properties of the mixed metal oxide are controlled by (and depend on) the properties of the metal precursor or lithium salt precursor they are manufactured from. In a further aspect, the properties of the mixed metal oxide, thus controlled by the properties of the metal precursor or lithium salt precursor, are controlled to yield optimal properties of the lithium-selective ion exchange material. ForAttorney Docket No.: 733PCT601

[0060] example, the use of metal precursor controlled particle size distribution yields mixed metal oxides with controlled particle size distributions. In a further aspect, mixed metal oxides thus controlled yield lithium-selective ion exchange materials with controlled particle size distributions derived therefrom. For example, exemplary composition 8 (Table 1) has an advantageous particle size distribution that closely reflects the particle size distribution of the manganese dioxide precursor exemplary composition 4 (Table 1). In contrast, exemplary composition 9 has a disadvantageous particle size distribution that closely reflects the particle size distribution of the manganese dioxide precursor exemplary composition 3 (Table 1). Similar conclusions can be drawn from advantageous exemplary composition 5 (derived from exemplary composition 2), compared to disadvantageous exemplary composition 9 (derived from exemplary composition 1). In these embodiments, said advantageous particle size distribution lead to advantageous properties, including but not limited to the high specific surface area, high pore volume, low pressure drop and fast settling velocity.

[0061]

[0027] It is thus critical to control the properties of metal precursors used in the manufacturing of lithium-selective ion exchange materials to yield optimal mixed metal oxides and lithiumselective ion exchange materials derived therefrom. For example, compositions disclosed herein comprise mixed metal oxides derived from titanium oxide and manganese oxide precursor (exemplary compositions 1 to 4 in Table 1) which exhibit high surface area, porosity, and advantageous particle size distributions. Other precursor without said advantageous properties, including salts or liquid (such as titanium alkoxides, manganese carbonate, manganese acetate, manganese hydroxide, manganese nitrate, manganese sulfate, manganese phosphate, or any other ionic titanium or manganese salts) may result in disadvantageous particle size distributions, low surface area, and low porosity, leading to disadvantageous compositions of mixed metal oxides synthesized therefrom, and lithium-selective ion exchange materials derived therefrom.

[0062] Key Terms and Definitions

[0063]

[0028] As used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “an agent” includes a plurality of such agents, and reference to “the cell” includes reference to one or more cells (or to a plurality of cells) and equivalents thereof known to those skilled in the art, and so forth. When ranges are used herein for physical properties, such as molecular weight, or chemical properties, such as chemical formulae, all combinations andAttorney Docket No.: 733PCT601

[0064] subcombinations of ranges and specific embodiments therein are intended to be included. The term “about” when referring to a number or a numerical range means that the number or numerical range referred to is an approximation within experimental variability (or within statistical experimental error), and thus the number or numerical range, in some instances, will vary between 1% and 15% of the stated number or numerical range. The term “comprising” (and related terms such as “comprise” or “comprises” or “having” or “including”) is not intended to exclude that in other certain embodiments, for example, an embodiment of any composition of matter, composition, method, or process, or the like, described herein, “consist of’ or “consist essentially of’ the described features.

[0065]

[0029] The terms “lithium”, “lithium ion”, and “Li+” are used interchangeably in the present specification and these terms are synonymous unless specifically noted to the contrary. The terms “hydrogen”, “hydrogen ion”, “proton”, and “H+” are used interchangeably in the present specification and these terms are synonymous unless specifically noted to the contrary.

[0066]

[0030] As used herein, the words “column” and “vessel” are used interchangeably. In some embodiments described herein referring to a “vessel”, the vessel is a column. In some embodiments described herein referring to a “column”, the column is a vessel.

[0067]

[0031] The term “the pH of the system” or “the pH of’ a component of a system, for example one or more tanks, vessels, columns, pH modulating units, or pipes used to establish fluid communication between one or more tanks, vessels, columns, or pH modulating units, refers to the pH of the liquid medium contained or present in the system, or contained or present in one or more components thereof. In some embodiments, the liquid medium contained in the system, or one or more components thereof, is a liquid resource. In some embodiments, the liquid medium contained in the system, or one or more components thereof, is a brine. In some embodiments, the liquid medium contained in the system, or one or more components thereof, is an acid solution, an aqueous solution, a wash solution, a salt solution, a salt solution comprising lithium ions, or a lithium-enriched solution. As used herein, pH is equal to the negative logarithmic value of the concentration of protons in the aqueous solution. The pH of the solutions described herein are preferably determined with a pH probe. However, many of the solutions described herein comprise high concentrations of ions (e.g., sodium) that are known to interfere with pH probe sensors. Therefore, solutions with high ion concentrations can lead to shifted readings. In such cases, pH probe values are confirmed by diluting the test solution, for example by 10X or 100X, and remeasuring via pH probe to ensure that the change in pH is consistent with the change in concentration of protons. Alternative methods of pH determination include chemical tests such as titration with colored indicators or litmus tests.Attorney Docket No.: 733PCT601

[0068]

[0032] The term “concentration”, as used herein, refers to the amount of a chemical species within a given amount of liquid. In some embodiments, said concentration can be specified as the mass of a species dissolved in an amount of liquid (e.g. mg / L, herein used interchangeably with ppm), or the number of moles of a species dissolved in an amount of liquid (e.g. mol / L). In some embodiments, concentration can be specified by the ratio of moles or mass of the species of interest to one or more other species dissolved in the same liquid. In some embodiments, only the mass concentration of an ionic species is stated; for example, a concentration of sodium (Na) is stated to be 100 milligrams per liter (mg / L). In such cases, the stated concentration refers to the mass concentration of the ion in solution, and does not include the mass of the anion; in the example stated above, such an ion may comprise chloride (C1-), nitrate (NO3 ), or sulfate (SO42).

[0069]

[0033] As used herein, the term “synthetic lithium solution” describes a solution comprising lithium that is not present in nature and obtained by a process for processing, refining, recovering or purifying lithium. In some embodiments, a synthetic lithium solution can be yielded by placing an acid into contact with a lithium-selective ion exchange material. In some embodiments, a synthetic lithium solution is a lithium eluate. In some embodiments, a synthetic lithium solution is used in place of a liquid resource. In some embodiments, a synthetic lithium solution is combined with a liquid resource. In some embodiments, a synthetic lithium solution is a leachate solution (e.g., a leachate of one or more ores, a leachate of one or more minerals, a leachate of one or more clays, a leachate of waste or recycled materials comprising lithium). In some embodiments, a synthetic lithium solution is a brine concentrated by solar evaporation.

[0070]

[0034] The term “direct lithium extraction,” as used herein, refers to a process involving the sorption or adsorption of lithium from solution. Direct lithium extraction can be carried out with a lithium-selective ion exchange material.

[0071]

[0035] The term “eluent,” as used herein, refers to a liquid input employed for the removal of lithium from a lithium-selective ion exchange material. An eluent can be acidic. An eluent that has been placed in contact with a lithium-selective ion exchange material that releases lithium to yield an “eluate”. Said eluate is a lithium eluate. A lithium eluate is a synthetic lithium solution. A synthetic lithium solution is a lithium eluate. In some embodiments, the eluent or eluate is an acidic solution. In such cases, the protons of the acidic eluate displace the lithium on the ion exchange material to yield a synthetic lithium eluate.

[0072]

[0036] As used herein, the term “lithium purity” refers to the chemical purity of a lithium chemical, lithium compound, or a solution that comprises lithium or a lithium compound. In some embodiments, lithium purity can be expressed as the percentage of lithium in a solution as on the basis of the total metal ion content of the solution. In some embodiments, lithium purity isAttorney Docket No.: 733PCT601

[0073] expressed in terms of the quantities or percentages of specific impurities that may be present in a lithium compound or a solution that comprises lithium.

[0074]

[0037] As used herein, the term “lithium recovery’’ refers to the fraction or percent of lithium atoms present in the liquid resource that are extracted therefrom by the lithium-selective ion exchange material. In some embodiments, said lithium atoms are released by treatment of the ion exchange material with acid, yielding a synthetic lithium solution.

[0075]

[0038] As used herein, the term “process fluid’’ refers to any liquid or solution that used in any step or process according to the methods and systems for lithium recovery from a liquid resource as described herein. In some embodiments, the process fluid is the liquid resource. In some embodiments, the process fluid is the adjusting fluid. In some embodiments, the process fluid is the raffinate. In some embodiments, the process fluid is water. In some embodiments, the process fluid is acid (e.g., an acidic solution, a solution comprising acid). In some embodiments, the process fluid is base (e.g., a basic solution, a solution comprising base).

[0076]

[0039] As used herein, the term “buffer” refers to a solution that can resist pH change upon the addition of an acidic or basic components. A buffer can neutralize small amounts of added acid or base, thus maintaining the pH of a solution comprising the buffer. In some embodiments, a buffer is a solution comprising a weak acid and a salt of the corresponding conjugate base. In some embodiments, a buffer is a solution comprising a weak base and a salt of the corresponding conjugate acid. A non-limiting example of a buffer is a solution of boric acid and sodium hydroxide.

[0077]

[0040] The term “mother liquor,” as used herein, is a liquid byproduct of a process for the generation of solid compound via crystallization from a solution containing the chemical components of said solid compound. In one exemplary embodiment, lithium carbonate is crystallized from a solution comprising lithium and carbonate ions; the remaining liquid is referred to as a mother liquor, and contains some remaining lithium and carbonate ions, together with additional salts that did not precipitate to form the solid.

[0078]

[0041] The term “calcination,” as used herein, refers to the thermal treatment of solid chemical compounds, wherein the compound is raised to a high temperature to result in a desirable chemical or physical change. In some embodiments, said change involves a chemical reaction to produce a new chemical compound. In some exemplary embodiments described herein, calcination of a mixture comprising a lithium salt precursor and a metal precursor results in the formation of a mixed metal compound. In some embodiments, the one or more chemical compounds in the mixture may melt throughout the calcination treatment. In some embodiments, the one or more chemical compounds in the mixture may remain solid throughout the calcinationAttorney Docket No.: 733PCT601

[0079] treatment. In some embodiments, the gaseous atmosphere throughout the calcination process is controlled. In some embodiments, said atmosphere is inert. In some embodiments, the oxygen content in said atmosphere is controlled. In some embodiments, the temperature of the calcination process is constant. In some embodiments, the temperature of the calcination process is higher than 250 °C.

[0080]

[0042] As used herein, certain chemical species are denoted by a chemical formula which includes x as a subscript. Examples of such species include NOx, SOx, COx. The subscript x indicates that the chemical species comprise one or more possible individual molecules with different possible numbers of oxygen atoms. In some embodiments, x is an integer; in other embodiments, x a fraction or non-integer number. In some embodiments, said individual molecules occur as a mixture. In some embodiments, said individual molecules may interconvert. For example, NOx refers to either NO (nitric oxide) or NO2 (nitrogen dioxide), two common gases, which may interconvert by, for example, the action of light and ozone in the atmosphere. By analogy, SOx refers to SO, S2O2, SO2, SO3, SO4, S2O (or SO1 / 2), among other chemical species. These chemical species, in some embodiments, include by-product gases generated by the methods and systems described herein.

[0081]

[0043] As used herein, particle sizes are expressed by a characteristic dimension, where characteristic dimension will be understood to refer to a dimension that reasonably represents the size of a particle to one skilled in the art. In certain embodiments, characteristic dimension is measured as the diameter for spherical or semi-spherical particles. In certain embodiments, such as those described with respect to the disclosed examples, diameters (e.g., effective diameters, average diameters) are characterized by laser diffraction particle sizing whereby the utilized instrument(s) and software may model the shape of the analyzed particles as spherical. Particle sizes can be classified by cut off points, typically referred to as a DXX, DXX, or dXX value, where XX is a number from 1 to 99. XX refers to the percentage of particles that are smaller than the DXX value, most commonly measured on a volume- weighted basis. For example, a d97 value of 100 microns indicates that 97% of the total particle volume in the sample consists of particles smaller than 100 microns. Similarly, a dlO value of 10 microns indicates that 10% of the total particle volume consists of particles smaller than 10 microns. In another usage of the above definition, the parameter D50 specifies that 50% of the particle volume consists of particles larger than the specified value, and 50% of the particle volume consists of particles smaller than the specified value. In some embodiments described herein, the same terminology is applied to the sizes of pores; in such usage, the parameter D50 specifies that 50% of the pore volume is larger than the specified value, and 50% of the pore volume is smaller than theAttorney Docket No.: 733PCT601

[0082] specified value. In some embodiments, a fraction - measured in % - of the particles is exhibit a characteristic diameter; unless otherwise stated, said % will be understood to denote the weight percentage (wt%) of particles. In some embodiments, the density of particles is constant independent of their characteristic diameter; thus, for these embodiments, wt% and volume % are equivalent.

[0083]

[0044] As used herein, the term "particle" refers to a discrete physical unit of material that is not easily separable. The measured dimension of this discrete physical unit is referred to as the particle size. In some embodiments, a physical classification system with discrete openings, such as a sieve, allows a particle with a dimension similar or smaller to such an opening to pass through. Consequently, in some embodiments, the particle size may refer to secondary particles, which are aggregates of smaller primary particles that are chemically or physically bound together to form a larger secondary unit. In some embodiments, the characteristic dimension used for classification represents the size of the secondary particle as a whole. In other embodiments, the characteristic dimension may correspond to the size of primary particles.

[0084]

[0045] The section headings used herein are for organizational purposes only and are not to be construed as limiting the subject matter described or preclude the combination of the subject matter of the disclosure under any one section heading with any other subject matter of the disclosure under any other section heading or any other subject matter of the disclosure.

[0085] Embodiments described herein with any one or more features can be readily combined with the features of any embodiments described further herein. Embodiments described herein are not limiting so as to wholly describe all embodiments of the disclosure.

[0086] Key definitions regarding the measurement and description of particle properties

[0046] As used herein, particle sizes are expressed by a characteristic dimension, where characteristic dimension will be understood to refer to a dimension that reasonably represents the size of a particle to one skilled in the art. For example, said characteristic dimension is typically measured as the diameter for spherical or semi-spherical particles. Particle sizes can be classified by cut off points, typically referred to as a DXX, Dxx, or dXX value, where XX is a number from 1 to 99. XX refers to the percentage of particles that are smaller than the DXX value, most commonly measured on a volume-weighted basis. For example, a d97 value of 100 microns indicates that 97% of the total particle volume in the sample consists of particles smaller than 100 microns. Similarly, a dlO value of 10 microns indicates that 10% of the total particle volume consists of particles smaller than 10 microns. In another usage of the above definition, theAttorney Docket No.: 733PCT601

[0087] parameter D50 specifies that 50% of the particle volume consists of particles larger than the specified value, and 50% of the particle volume consists of particles smaller than the specified value.

[0088]

[0047] In some embodiments described herein, the same terminology is applied to the sizes of pores; in such usage, the parameter D50 specifies that 50% of the pore volume is larger than the specified value, and 50% of the pore volume is smaller than the specified value.

[0089]

[0048] It is recognized that measurements of average particle diameter can vary according to the method of determination utilized. Determination of said average particle diameter according to one method to obtain one or more values shall be understood to inherently encompass all other values that may be obtained using other methods. The average particle diameter can be determined using sieve analysis. The average particle diameter can be determined using optical microscopy. The average particle diameter can be determined using electron microscopy. The average particle diameter can be determined using laser diffraction. In some embodiments, the average particle diameter is determined using laser diffraction, wherein a Bettersizer ST instrument is used. In some embodiments, the average particle diameter is determined using a Bettersizer ST instrument. In some embodiments, the average particle diameter is determined using laser diffraction, wherein an Anton-Parr particle size analyzer (PSA) instrument is used. In some embodiments, the average particle diameter is determined using an Anton-Parr PSA instrument. In some embodiments, the average particle diameter is determined using laser diffraction, wherein a Malvern Panalytical Mastersizer particle size analyzer instrument is used. In some embodiments, the average particle diameter is determined using a Malvern Panalytical Mastersizer particle size analyzer instrument. The average particle diameter can be determined using dynamic light scattering. The average particle diameter can be determined using static image analysis. The average particle diameter can be determined using dynamic image analysis.

[0090]

[0049] In some embodiments, the composition of the mixed metal oxide, matrix-particle mixture, composite structures, or lithium-selective ion exchange material measured by an analytical technique. In some embodiments, said analytical technique comprises dissolving the mixed metal oxide or lithium-selective ion exchange material to dissolve it in a liquid, and measuring the concentration of lithium and transition metal in this solution. In some embodiments, the acid is nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, and aqueous solution thereof, or combinations thereof. In some embodiments, the concentration is measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES), inductively coupled plasma optical emission spectroscopy (ICP-OES), or inductively coupled plasma mass spectrometry (ICP-MS). It will be understood that synthesis methods, sample preparationAttorney Docket No.: 733PCT601

[0091] techniques, and compositional measurements involve certain heterogeneity and variability across samples, which may cause measured compositions to deviation from the stoichiometric composition of samples described and disclosed herein. Therefore, compositions with elemental compositions measured to be within 15% of the theoretical molar compositions described herein shall be considered to comprise said theoretical molar compositions. Additional techniques, such as X-ray diffraction, can further be used to confirm and determine the structure and composition of the material compositions described herein.

[0092]

[0050] Embodiments of materials described herein include controlling the size of particles of said materials. It shall be understand that the terms “controlling the size”, “classification”, “sizing”, processing through a “classification device”, or related terms apply to particles of any materials disclosed herein, including lithium-selective ion exchange materials, lithium salt precursor(s), metal precursor(s), mixed metal oxide(s), matrix material(s), structures, composite structures, comminuted composite structures, or any intermediates in the preparation or synthesis of any of the materials described herein.

[0093]

[0051] As used herein, textural properties refer to the physical attributes of a material's surface and internal structure. These properties include, but are not limited to, surface area, pore size distribution, and porosity. In some embodiments, surface area is measured by the Brunauer-Emmett-Teller (BET) method from nitrogen physisorption data. In some embodiments, pore size distribution is determined using Barrett-Joyner-Halenda (BJH) analysis. In some embodiments, including all examples in Table 1, porosity is assessed through nitrogen physisorption. In some embodiments, porosity can also be assessed by mercury intrusion porosimetry.

[0094]

[0052] As used herein, the term physicochemical properties refers to the inherent physical and chemical characteristics of a material. These properties include but are not limited to, thermal stability, porosity, surface area, chemical composition, crush strength, attrition resistance, pore size distribution, and crystallinity. In some embodiments, thermal stability is evaluated using thermogravimetric analysis (TGA). In some embodiments, chemical composition is determined through techniques such as inductively coupled plasma mass spectrometry (ICP-MS) and X-ray diffraction (XRD) is used to assess crystallinity. In some embodiments, textural properties are also physicochemical properties.

[0095]

[0053] As used herein, the performance of a material for lithium extraction refers to its ability efficiently extract lithium from a liquid resource. In some embodiments, said performance can be assessed by its lithium ion exchange capacity (mg of Li uptake per g of material), selectivity for lithium uptake, purity of eluted lithium product, recovery of lithium (% lithium recovered relative to that present in the liquid resource), and kinetics of lithium uptake. In someAttorney Docket No.: 733PCT601

[0096] embodiments, ion exchange capacity is measured using batch equilibrium experiments. In some embodiments, selectivity coefficient is determined through competitive ion exchange studies, and kinetic performance is evaluated through dynamic column experiments.

[0097] General overview of disclosed compositions of lithium-selective ion-exchange materials

[0054] Lithium-selective ion exchange materials are crucial for efficient extraction and purification of lithium from various sources and liquid resources. These materials can be engineered to selectively capture lithium ions from complex mixtures, significantly improving the yield and purity of lithium.

[0098]

[0055] A major challenge for lithium extraction using lithium-selective ion exchange materials is achieving material compositions with properties that result in the optimal extraction process for lithium. Optimal extraction processing includes, but is not limited to, achieving high recovery of lithium, high lithium product purity, and low degradation of the ion exchange material when extracting lithium form a variety of liquid resources. Optimal extraction processing also includes incorporation of the lithium-selective ion exchange material into systems for commercial lithium extraction. Such systems and processes often require advantageous hydrodynamic properties of lithium-selective ion exchange materials, which makes said materials suitable for flowing liquids, including liquid resources and acids, over packed beds or fluidized beds of ion exchange materials. Such systems and processes often require specific hydrodynamic properties that make said ion-exchange materials amenable to transport and conveyance through systems for lithium extraction.

[0099]

[0056] There is a need therefore for compositions of lithium-selective ion exchange materials with optimal properties for processing of liquid resources for lithium extraction. Herein, compositions of lithium-selective ion exchange materials, and systems, methods, and processes for their manufacture are disclosed. Said compositions result in optimal physicochemical, textural, and hydrodynamic properties of said lithium-selective ion exchange materials, which result in their efficient use in commercial lithium extraction systems.

[0100]

[0057] An aspect of the invention disclosed herein is a composition of a lithium-selective ion exchange material, the composition comprising particles of a mixed metal oxide, wherein the mixed metal oxide comprises lithium and at least one transition metal. In some embodiments, said transition metal is selected from the group consisting of titanium, manganese, iron, aluminum, tin, or vanadium. In some embodiments, the molar ratio of lithium to transition metal ranges from 0.25:1 to 4:1.Attorney Docket No.: 733PCT601

[0101]

[0058] In some embodiments, the particles of the mixed metal oxide are coated by, embedded in, adhered to, or otherwise supported by the one or more matrix materials. In some embodiments, said matrix materials serve to protect the mixed metal oxide from degradation by the liquid resource or acidic eluent solution. In some embodiments, said matrix materials serve to form larger secondary particles or aggregates from the primary mixed metal oxide particles, resulting in advantageous textural or hydrodynamic properties.

[0102]

[0059] In some embodiments, the lithium-selective ion exchange material composition exhibits advantageous textural and hydrodynamic properties, including advantageous pore volumes, pore sizes, surface areas, and particle size distributions. In an aspect, disclosed herein are compositions of a lithium-selective ion exchange material comprising particles of a mixed metal oxide with said advantageous physicochemical, textural, and hydrodynamic properties which include: a molar ratio of lithium to a transition metal, specific pore volume, specific surface area, particle size distributions (including d5, dlO, d90, d95, and -400M%), pressure drops, and settling velocities. In some embodiments, the compositions of lithium-selective ion exchange material comprise particles of a mixed metal oxide and one or more matrix material(s), wherein said compositions exhibit specific textural and physicochemical properties. In some embodiments, said physicochemical, textural, and hydrodynamic properties result from the manufacturing process used for production of the lithium-selective ion exchange material. In some embodiments, said physicochemical, textural, and hydrodynamic properties result from the physicochemical, textural, and hydrodynamic properties of mixed metal oxide and / or matrix material used to manufacture the lithium-selective ion exchange material. In some embodiments, said physicochemical, textural, and hydrodynamic properties (“properties”) result from the properties of mixed metal oxide used to manufacture the lithium-selective ion exchange material, and the properties of mixed metal oxide themselves depend on the properties of the metal precursor and / or lithium salt precursor used to manufacture the mixed metal oxide. As such, the properties of the lithium-selective ion exchange material compositions disclosed herein are a result of the metal precursor, lithium salt precursor, matrix material, and / or mixed metal oxide used to manufacture said material.

[0103]

[0060] Herein, methods, processes, and systems used for the manufacture of said lithiumselective ion exchange materials are disclosed. In some methods, the particle size distribution of the metal precursor, lithium salt precursor, matrix material, lithium-selective ion exchange material, or a combination thereof, is controlled. Said control of particle sizes, and said processes and methods, serve to yield advantageous compositions of lithium-selective ion exchange materials. As used herein, the term “controlling” or “control” of a particle size can alsoAttorney Docket No.: 733PCT601

[0104] refer to the processes used to control said particle size. Such processes are alternatively referred to a “classification” or “classifying” (of the particles by size), or “sizing” or “to size” (the particles); it shall be understood that embodiments described with reference to only one of this terms equally apply to “controlled”, “classified” or otherwise “sized” particles.

[0105]

[0061] In an aspect, the properties of the metal precursor, lithium salt precursor, matrix material, and / or mixed metal oxide are controlled to yield optimal properties of the lithium-selective ion exchange material. In a related aspect, the properties of the lithium-selective ion exchange material are controlled by (and depend on) the properties of the metal precursor, lithium salt precursor, matrix material, and / or mixed metal oxide they are manufactured from. In a further aspect, the properties of the mixed metal oxide are controlled to yield optimal properties of the lithium-selective ion exchange material. For example, the use of mixed metal oxide with high specific surface areas yields a lithium-selective ion exchange material with a high specific surface area, as exemplified in exemplary compositions 5 and derived composition 15. In yet another example, the use of mixed metal oxide with high specific pore volume yields a lithiumselective ion exchange material with a high specific pore volume, as exemplified in exemplary compositions 5 and derived composition 15.

[0106]

[0062] In one aspect, the lithium-selective ion exchange material comprises particles of the mixed metal oxide on their own (i.e. without an optional matrix material). In some embodiments, the mixed metal oxide comprises lithium and a transition metal, wherein said transition metal is selected from titanium or manganese. Thus, the properties of the lithium-ion exchange material correspond to those of the mixed metal oxide. In some embodiments, the mixed metal oxide exhibits a controlled particle size distribution, as in exemplary compositions 4 to 8 in table 1; thus, the lithium-selective ion exchange material composition resulting in using said mixed metal oxide as an ion exchange material exhibit these controlled and advantageous particle size distributions. In these embodiments, said advantageous particle size distribution lead to advantageous properties, including but not limited to the high specific surface area, high pore volume, low pressure drop and fast settling velocity.

[0107]

[0063] In an aspect, the properties of the metal precursor or lithium salt are controlled to yield optimal properties of the mixed metal oxide. In a related aspect, the properties of the mixed metal oxide are controlled by (and depend on) the properties of the metal precursor or lithium salt precursor they are manufactured from. In a further aspect, the properties of the mixed metal oxide, thus controlled by the properties of the metal precursor or lithium salt precursor, are controlled to yield optimal properties of the lithium-selective ion exchange material. For example, the use of metal precursor controlled particle size distribution yields mixed metalAttorney Docket No.: 733PCT601

[0108] oxides with controlled particle size distributions. In a further aspect, mixed metal oxides thus controlled yield lithium-selective ion exchange materials with controlled particle size distributions derived therefrom. For example, exemplary composition 8 (Table 1) has an advantageous particle size distribution that closely reflects the particle size distribution of the manganese dioxide precursor exemplary composition 4 (Table 1). In contrast, exemplary composition 9 has a disadvantageous particle size distribution that closely reflects the particle size distribution of the manganese dioxide precursor exemplary composition 3 (Table 1). Similar conclusions can be drawn from advantageous exemplary composition 5 (derived from exemplary composition 2), compared to disadvantageous exemplary composition 9 (derived from exemplary composition 1). In these embodiments, said advantageous particle size distribution lead to advantageous properties, including but not limited to the high specific surface area, high pore volume, low pressure drop and fast settling velocity.

[0109]

[0064] It is thus critical to control the properties of metal precursors used in the manufacturing of lithium-selective ion exchange materials to yield optimal mixed metal oxides and lithiumselective ion exchange materials derived therefrom. For example, compositions disclosed herein comprise mixed metal oxides derived from titanium oxide and manganese oxide precursor (exemplary compositions 1 to 4 in Table 1) which exhibit high surface area, porosity, and advantageous particle size distributions. Other precursor without said advantageous properties, including salts or liquid (such as titanium alkoxides, manganese carbonate, manganese acetate, manganese hydroxide, manganese nitrate, manganese sulfate, manganese phosphate, or any other ionic titanium or manganese salts) may result in disadvantageous particle size distributions, low surface area, and low porosity, leading to disadvantageous compositions of mixed metal oxides synthesized therefrom, and lithium-selective ion exchange materials derived therefrom.

[0110]

[0065] In the sections and examples that follow, general embodiments of the present disclosure, including composition of lithium-selective ion exchange materials, manufacturing methods thereof, and uses thereof, are disclosed.

[0111] Compositions of mixed metal oxides, lithium-selective ion-exchange materials derived therefrom, and methods and systems for preparing the same

[0112]

[0066] An aspect of the present disclosure are compositions comprising, and systems and methods for preparing, a mixed metal oxide. Exemplarily embodiments of the present disclosure are provided in Table 1 and examples therefrom.Attorney Docket No.: 733PCT601

[0113]

[0067] An aspect of the invention disclosed herein is a composition of a lithium-selective ion exchange material, the composition comprising particles of a mixed metal oxide, wherein the mixed metal oxide comprises lithium and at least one transition metal. In some embodiments, said transition metal is selected from the group consisting of titanium, manganese, iron, aluminum, tin, or vanadium. In some embodiments, the molar ratio of lithium to transition metal ranges from 0.25:1 to 4:1.

[0114]

[0068] In some embodiments, the transition metal is selected from a group consisting of: titanium, manganese, iron, aluminum, tin, or vanadium. In some embodiments, the compositions comprises at least one transition metals selected from a group consisting of: titanium, manganese, iron, aluminum, tin, or vanadium.

[0115]

[0069] In some embodiments, the molar ratio of lithium to transition metal from about 0.25:1 to about 1:1, from about 1:1 to about 1:2, from about 1:2 to about 1:4. In some embodiments, the molar ratio of lithium is about 2:1, about 0.8:1, about 0.5:1, about 1:1, or about 3:1.

[0116]

[0070] Exemplary embodiments compositions of mixed metal oxide include, but are not limited to: LiFePCU, LiMnPCU, LiaTiOs. Li2Ti2O5, Li2MnOj, LiaMnaCF, LiaSnCU, Li4Ti50i2, Li4MnsOi2, LiTi2O4, LiMn2O4. Li1.6Mn1.6O4, LiAlCh, LiCuO2, LiTiO2, Li4TiO4, Li7TinO24, L13VO4, compounds thereof, nonstoichiometric compounds thereof, modifications thereof, solid solutions thereof, or a combination thereof.

[0117]

[0071] In some embodiments, a lithium-selective ion exchange material comprises a mixed metal oxide. In some embodiments, the mixed metal oxide comprises LiFePCU, LiMnPO4, Li2TiO3, Li2Ti2O5, Li2MnOs, Li2Mn2O5, Li2SnC>3, Li4TisOi, Li4MnsOi2, LiTi2O4, LiMn2O4, Li1.eMn1.6O4, LiA102, LiCuO2, LiTiO2, Li4TiO4, Li7TinO24, L13VO4, compounds thereof, nonstoichiometric compounds thereof, modifications thereof, solid solutions thereof, or a combination thereof.

[0118]

[0072] In some embodiments, a solid solution may refer to a single phase solution where all metallic grains (crystals) are of the same composition. In some embodiments, a solid solution may refer to a state in which two or more metal solids or non-metal solids are dissolved at an atomic level in each other and present as an entirely uniform solid phase, and may refer to a mixed crystal in some cases. In some embodiments, a solid solution may refer to an invasiontype solid solution in which elements smaller than the interval of crystal lattices are introduced, a substitution -type solid solution in which elements are replaced with parent phase atoms to be introduced, and the like by a dissolution method of solute atoms. In some embodiments, when forming a solid solution, some of the atoms occupying lattice positions may be statistically substituted with a different kind of atoms, without causing any changes in the crystal structure,Attorney Docket No.: 733PCT601

[0119] or a different kind of atoms that are statistically distributed in inter-lattice positions. For example, in a case in which the active materials are metal oxides, a plurality of kinds of metal oxide particles can be made to form a solid solution by mixing a plurality of kinds of metal oxides together, then, firing the metal oxides at a high temperature, and causing element diffusion in the contact interface.

[0120]

[0073] In some embodiments, the composition is LiFePO4, and the molar ratio of lithium to iron is about 1:1. In some embodiments, the composition is LiMnPO4, and the molar ratio of lithium to manganese is about 1:1. In some embodiments, the composition is Li2TiO3, and the molar ratio of lithium to titanium is about 2:1. In some embodiments, the composition is Li2Ti2O5, and the molar ratio of lithium to titanium is about 1:1. In some embodiments, the composition is Li2MnO3, and the molar ratio of lithium to manganese is about 2:1. In some embodiments, the composition is Li2Mn2O5, and the molar ratio of lithium to manganese is about 1:1. In some embodiments, the composition is Li2SnO3, and the molar ratio of lithium to tin is about 2:1. In some embodiments, the composition is Li4Ti5O12, and the molar ratio of lithium to titanium is about 4:5. In some embodiments, the composition is Li4Mn5O12, and the molar ratio of lithium to manganese is about 4:5. In some embodiments, the composition is LiTi2O4, and the molar ratio of lithium to titanium is about 1:2. In some embodiments, the composition is LiMn2O4, and the molar ratio of lithium to manganese is about 1:2. In some embodiments, the composition is Li1.6Mn1.6O4, and the molar ratio of lithium to manganese is about 1:1. In some embodiments, the composition is LiAlO2, and the molar ratio of lithium to aluminum is about 1:1. In some embodiments, the composition is LiCuO2, and the molar ratio of lithium to copper is about 1:1. In some embodiments, the composition is LiTiO2, and the molar ratio of lithium to titanium is about 1:1. In some embodiments, the composition is Li4TiO4, and the molar ratio of lithium to titanium is about 4:1. In some embodiments, the composition is Li7Ti11O24, and the molar ratio of lithium to titanium is about 7:11. In some embodiments, the composition is Li3VO4, and the molar ratio of lithium to vanadium is about 3:1.

[0121]

[0074] In some embodiments, the mixed metal oxide comprises LiFePO4, LiMnPO4, Li2TiO3, Li2MnO3, Li2SnO3, Li4Ti5O12, Li4Mn5O12, LiMn2O4, Li1.6Mn1.6O4, LiAlO2, LiCuO2, LiTiO2, Li4TiO4, Li7Ti11O24, Li3VO4, Li2Si3O7, Li2CuP2O7, LiNixMnyCo1-x-yO2, LiNixMnyAl1-x-yO2, modifications thereof, solid solutions thereof, or a combination thereof.

[0122]

[0075] In some embodiments, the mixed metal oxide reversibly exchanges lithium and hydrogen ions. In some embodiments, the mixed metal oxide is utilized as the active sorbent in a lithiumselective sorbent composite. In some embodiments, the mixed metal oxide is utilized as the active sorbent in a lithium-selective porous bead.Attorney Docket No.: 733PCT601

[0123]

[0076] In some embodiments, the mixed metal oxide may be used in energy storage applications as a cathode or anode material. In some embodiments, the mixed metal oxide may be used in lithium-ion batteries as a cathode or anode active material. In some embodiments, the mixed metal oxide may be used in sodium-ion batteries as a cathode or anode active material.

[0124]

[0077] In an aspect, disclosed herein are compositions of a lithium-selective ion exchange material comprising particles of a mixed metal oxide. In some embodiments, said compositions exhibit specific physicochemical, textural, and hydrodynamic properties which include: a molar ratio of lithium to a transition metal, specific pore volume, specific surface area, particle size distributions (including d5, dlO, d90, d95, and -400M%), pressure drops, and settling velocities. In some embodiments, the compositions of lithium-selective ion exchange material comprise particles of a mixed metal oxide and one or more matrix material(s), wherein said compositions exhibit specific textural and physicochemical properties. In some embodiments, said physicochemical, textural, and hydrodynamic properties result from the manufacturing process used for production of the lithium-selective ion exchange material. In some embodiments, said physicochemical, textural, and hydrodynamic properties result from the physicochemical, textural, and hydrodynamic properties of mixed metal oxide and / or matrix material used to manufacture the lithium-selective ion exchange material. In some embodiments, said physicochemical, textural, and hydrodynamic properties (“properties”) result from the properties of mixed metal oxide used to manufacture the lithium-selective ion exchange material, and the properties of mixed metal oxide themselves depend on the properties of the metal precursor and / or lithium salt precursor used to manufacture the mixed metal oxide. As such, the properties of the lithium-selective ion exchange material compositions disclosed herein are a result of the metal precursor, lithium salt precursor, matrix material, and / or mixed metal oxide used to manufacture said material.

[0125]

[0078] In an aspect, the properties of the metal precursor, lithium salt precursor, matrix material, and / or mixed metal oxide are controlled to yield optimal properties of the lithium-selective ion exchange material. In a related aspect, the properties of the lithium-selective ion exchange material are controlled by (and depend on) the properties of the metal precursor, lithium salt precursor, matrix material, and / or mixed metal oxide they are manufactured from. In a further aspect, the properties of the mixed metal oxide are controlled to yield optimal properties of the lithium-selective ion exchange material. For example, the use of mixed metal oxide with high specific surface areas yields a lithium-selective ion exchange material with a high specific surface area, as exemplified in exemplary compositions 5 and derived composition 15. In yet another example, the use of mixed metal oxide with high specific pore volume yields a lithium-Attorney Docket No.: 733PCT601

[0126] selective ion exchange material with a high specific pore volume, as exemplified in exemplary compositions 5 and derived composition 15.

[0127]

[0079] In one aspect, the lithium-selective ion exchange material comprises particles of the mixed metal oxide on their own (i.e. without an optional matrix material). In some embodiments, the mixed metal oxide comprises lithium and a transition metal, wherein said transition metal is selected from titanium or manganese. Thus, the properties of the lithium-ion exchange material correspond to those of the mixed metal oxide. In some embodiments, the mixed metal oxide exhibits a controlled particle size distribution, as in exemplary compositions 4 to 8 in table 1; thus, the lithium-selective ion exchange material composition resulting in using said mixed metal oxide as an ion exchange material exhibit these controlled and advantageous particle size distributions. In these embodiments, said advantageous particle size distribution lead to advantageous properties, including but not limited to the high specific surface area, high pore volume, low pressure drop and fast settling velocity.

[0128]

[0080] In an aspect, the properties of the metal precursor or lithium salt are controlled to yield optimal properties of the mixed metal oxide. In a related aspect, the properties of the mixed metal oxide are controlled by (and depend on) the properties of the metal precursor or lithium salt precursor they are manufactured from. In a further aspect, the properties of the mixed metal oxide, thus controlled by the properties of the metal precursor or lithium salt precursor, are controlled to yield optimal properties of the lithium-selective ion exchange material. For example, the use of metal precursor controlled particle size distribution yields mixed metal oxides with controlled particle size distributions. In a further aspect, mixed metal oxides thus controlled yield lithium-selective ion exchange materials with controlled particle size distributions derived therefrom. For example, exemplary composition 8 (Table 1) has an advantageous particle size distribution that closely reflects the particle size distribution of the manganese dioxide precursor exemplary composition 4 (Table 1). In contrast, exemplary composition 9 has a disadvantageous particle size distribution that closely reflects the particle size distribution of the manganese dioxide precursor exemplary composition 3 (Table 1). Similar conclusions can be drawn from advantageous exemplary composition 5 (derived from exemplary composition 2), compared to disadvantageous exemplary composition 9 (derived from exemplary composition 1). In these embodiments, said advantageous particle size distribution lead to advantageous properties, including but not limited to the high specific surface area, high pore volume, low pressure drop and fast settling velocity.

[0129]

[0081] It is thus critical to control the properties of metal precursors used in the manufacturing of lithium-selective ion exchange materials to yield optimal mixed metal oxides and lithium-Attorney Docket No.: 733PCT601

[0130] selective ion exchange materials derived therefrom. For example, compositions disclosed herein comprise mixed metal oxides derived from titanium oxide and manganese oxide precursor (exemplary compositions 1 to 4 in Table 1) which exhibit high surface area, porosity, and advantageous particle size distributions. Other precursor without said advantageous properties, including salts or liquid (such as titanium alkoxides, manganese carbonate, manganese acetate, manganese hydroxide, manganese nitrate, manganese sulfate, manganese phosphate, or any other ionic titanium or manganese salts) may result in disadvantageous particle size distributions, low surface area, and low porosity, leading to disadvantageous compositions of mixed metal oxides synthesized therefrom, and lithium-selective ion exchange materials derived therefrom.

[0131] Mixtures of a lithium salt precursor with a metal precursor

[0132]

[0082] An aspect of the invention disclosed herein is a composition of a lithium-selective ion exchange material, the composition comprising particles of a mixed metal oxide, wherein the mixed metal oxide comprises lithium and at least one transition metal. In some embodiments, said transition metal is selected from the group consisting of: titanium, manganese, iron, aluminum, tin, or vanadium. In some embodiments, the molar ratio of lithium to transition metal ranges from 0.25:1 to 4:1.

[0133]

[0083] In an aspect, the mixed metal oxide is prepared by a method comprising: (a) contacting a lithium salt precursor with a metal precursor to generate a synthesis mixture; (b) heating said synthesis mixture to form the mixed metal oxide.

[0134]

[0084] In an aspect of the disclosure, a lithium salt precursor, a metal precursor, or combinations thereof may be selected for optimized production of a mixed metal oxide. In some embodiments, the specific precursor may be selected for its low cost, its melting temperature, its supply chain availability, its production as an intermediate in separate processes, the materials performance characteristics it enables in the product mixed metal oxide, or combinations thereof. For example, lithium nitrate has a low melting point temperature and readily forms a molten salt flux when used as a precursor in calcination processes to produce mixed metal oxides. Conversely, lithium sulfate is a common intermediate in lithium-ion battery hydrometallurgical recycling processes, clay and hard rock lithium leach mining processes, and direct lithium extraction processes.

[0135]

[0085] In an aspect of the disclosure, a lithium salt precursor is contacted with a metal precursor to generate a synthesis mixture. In some embodiments, the lithium salt precursor comprisesAttorney Docket No.: 733PCT601

[0136] lithium nitrate, lithium sulfate, lithium carbonate, lithium hydroxide, lithium phosphate, sodium nitrate, sodium sulfate, sodium carbonate, sodium hydroxide, sodium phosphate, lithium nitrite, lithium sulfite, sodium nitrite, sodium sulfite, modifications thereof, solid solutions thereof, or combinations thereof. In some embodiments, the lithium salt precursor comprises anions. In some embodiments, the anions comprises nitrate, sulfate, carbonate, hydroxide, phosphate, nitrite, sulfite, or combinations thereof.

[0137]

[0086] In some embodiments, the metal precursor comprises titanium dioxide, titanium alkoxides, manganese dioxide, manganese oxide, manganese carbonate, manganese acetate, manganese hydroxide, tin oxide, tin acetate, tin sulfate, copper oxide, aluminum oxide, vanadium oxide, silicon dioxide, manganese nitrate, manganese sulfate, manganese phosphate, iron phosphate, ferric nitrate, ferric sulfate, ferrous nitrate, ferrous sulfate, iron oxide, cobalt oxide, NixMnyCo1-x-y(OH)2, NixMnyAl1-x-y(OH)2, solid solutions thereof, or combinations thereof. In some embodiments, the metal precursor is produced or refined by chemical, sol-gel, electrolytic, carbothermic, hydrothermal, hydrometallurgical, or pyrometallurgical processes, or a combination thereof. In some embodiments, the metal precursor is chemical manganese dioxide or electrolytic manganese dioxide. In some embodiments, the metal precursor is titanium dioxide, and the phase of said titanium dioxide comprises rutile, anatase, or a mixture thereof. In some embodiments, the titanium dioxide is produced by the chloride process, the sulfate process, or the Becher process.

[0138]

[0087] In some embodiments, the lithium salt precursor is lithium nitrate and the metal precursor is titanium dioxide. In some embodiments, the lithium salt precursor is lithium sulfate and the metal precursor is titanium dioxide.

[0139]

[0088] In some embodiments, the lithium salt precursor is lithium nitrate and the metal precursor is manganese hydroxide. In some embodiments, the lithium salt precursor is lithium sulfate and the metal precursor is manganese hydroxide.

[0140]

[0089] In some embodiments, the lithium salt precursor is lithium nitrate and the metal precursor is manganese carbonate. In some embodiments, the lithium salt precursor is lithium sulfate and the metal precursor is manganese carbonate. In some embodiments, the lithium salt precursor is lithium nitrate and the metal precursor is manganese dioxide.

[0141]

[0090] In some embodiments, the lithium salt precursor is lithium sulfate and the metal precursor is manganese dioxide. In some embodiments, the lithium salt precursor is lithium nitrate and the metal precursor is manganese nitrate. In some embodiments, the lithium salt precursor is lithium carbonate and the metal precursor is manganese nitrate.Attorney Docket No.: 733PCT601

[0142]

[0091] In some embodiments, the lithium salt precursor is lithium hydroxide and the metal precursor is manganese nitrate. In some embodiments, the lithium salt precursor is lithium sulfate and the metal precursor is manganese sulfate. In some embodiments, the lithium salt precursor is lithium carbonate and the metal precursor is manganese sulfate. In some embodiments, the lithium salt precursor is lithium hydroxide and the metal precursor is manganese sulfate.

[0143]

[0092] In some embodiments, the lithium salt precursor is lithium nitrate and the metal precursor is tin oxide. In some embodiments, the lithium salt precursor is lithium sulfate and the metal precursor is tin oxide.

[0144]

[0093] In some embodiments, the lithium salt precursor is lithium nitrate and the metal precursor is copper oxide. In some embodiments, the lithium salt precursor is lithium sulfate and the metal precursor is copper oxide.

[0145]

[0094] In some embodiments, the lithium salt precursor is lithium nitrate and the metal precursor is manganese phosphate. In some embodiments, the lithium salt precursor is lithium sulfate and the metal precursor is manganese phosphate. In some embodiments, the lithium salt precursor is lithium phosphate and the metal precursor is manganese nitrate. In some embodiments, the lithium salt precursor is lithium phosphate and the metal precursor is manganese sulfate.

[0146]

[0095] In some embodiments, the lithium salt precursor is lithium nitrate and the metal precursor is iron phosphate. In some embodiments, the lithium salt precursor is lithium sulfate and the metal precursor is iron phosphate. In some embodiments, the metal salt is lithium phosphate and the metal precursor is ferrous nitrate. In some embodiments, the metal salt is lithium phosphate and the metal precursor is ferrous sulfate.

[0147]

[0096] In some embodiments, the lithium salt precursor is lithium nitrate and the metal precursor is a mixture of iron phosphate and manganese phosphate. In some embodiments, the lithium salt precursor is lithium sulfate and the metal precursor is a mixture of iron phosphate and manganese phosphate. In some embodiments, the metal salt is lithium phosphate and the metal precursor is a mixture of ferrous nitrate and manganese nitrate. In some embodiments, the metal salt is lithium phosphate and the metal precursor is a mixture of ferrous sulfate and manganese sulfate.

[0148]

[0097] Cationic molar ratio as described here refers to the molar ratio of cations contributed by the lithium salt precursor to the cations contributed by the metal precursor. For example, a mixture of lithium nitrate (LiNO₃) and titanium dioxide (TiO₂) with a cationic ratio of 1:1 would have 1 mole of lithium nitrate for every mole of TiO₂. Conversely, mixture of lithium sulfateAttorney Docket No.: 733PCT601

[0149] (Li₂SO₄) and titanium dioxide (TiO₂) with a cationic ratio of 1:1 would have 0.5 moles of lithium nitrate for every mole of TiO₂. A mixture of lithium salt precursor lithium sulfate (Li2SO4) and 1:1 manganese phosphate / iron phosphate would have 1 mole of lithium sulfate, 1 mole of manganese phosphate and 1 mole of iron phosphate.

[0150]

[0098] In some embodiments, the cationic molar ratio of lithium salt precursor to metal precursor is from about 0.7:1 to about 0.8:1. In some embodiments, the cationic molar ratio of lithium salt precursor to metal precursor is from about 0.8: 1 to about 0.9:1. In some embodiments, the cationic molar ratio of lithium salt precursor to metal precursor is from about 0.9:1 to about 1:1. In some embodiments, the cationic molar ratio of lithium salt precursor to metal precursor is from about 1:1 to about 1:1.5. In some embodiments, the cationic molar ratio of lithium salt precursor to metal precursor is from about 2: 1 to about 1:1. In some embodiments, the cationic molar ratio of lithium salt precursor to metal precursor is from about 3:1 to about 2:1. In some embodiments, the cationic molar ratio of lithium salt precursor to metal precursor is from about 4:1 to about 3:1.

[0151]

[0099] In some embodiments, the mixture is mixed with a ribbon blender, a v-blender, a vertical cone screw blender, a tumble blender, or combinations thereof. In some embodiments, the mixture is milled together in a ball mill, an attrition mill, a jet mill, or combinations thereof. In some embodiments, the mixture is mixed and stored under inert atmosphere, dry atmosphere, elevated temperatures, or combinations thereof.

[0152] Heating of mixtures to from a mixed metal oxide

[0153]

[0100] An aspect of the invention disclosed herein is a composition of a lithium-selective ion exchange material, the composition comprising particles of a mixed metal oxide, wherein the mixed metal oxide comprises lithium and at least one transition metal. An aspect of the invention disclosed herein is the preparation of said composition by a method comprising: (a) contacting a lithium salt precursor with a metal precursor to generate a synthesis mixture; heating said synthesis mixture to form the mixed metal oxide. In some embodiments, said heating comprises a calcination process. Further aspects and embodiments related to heating said synthesis mixture or other materials disclosed herein are described herein.

[0154]

[0101] In one aspect, provided herein are compositions of lithium-selective ion exchange material. In a further aspect, provided herein are methods of preparing lithium-ion exchange materials. Is some embodiments, said method comprise a heating step. In some embodiments, said method comprises contacting a lithium salt precursor with a metal precursor to generate a synthesis mixture, and subjecting said mixture to a heating step comprising heating said synthesis mixture, to form the mixed metal oxide. In some embodiments, said step is describedAttorney Docket No.: 733PCT601

[0155] as a calcination step. It should be understood that calcination, heating, heat treatment(s), or heating step are therefore used interchangeably. It should be understood that embodiments of heat treatments for mixed metal oxide can similarly apply to lithium-selective ion exchange materials, or any other materials subject to such heat treatments.

[0156]

[0102] In some embodiments, calcination (e.g., a calcination process or heat treatment) occurs at from about 470 K to about 480 K, from about 480 K to about 490 K, from about 490 K to about 500 K, from about 500 K to about 510 K, from about 510 K to about 520 K, from about 520 K to about 530 K, from about 530 K to about 540 K, from about 540 K to about 550 K, from about 550 K to about 560 K, from about 560 K to about 570 K, from about 570 K to about 580 K, from about 580 K to about 590 K, from about 590 K to about 600 K, from about 600 K to about 610 K, from about 610 K to about 620 K, from about 620 K to about 630 K, from about 630 K to about 640 K, from about 640 K to about 650 K, from about 650 K to about 660 K, from about 660 K to about 670 K, from about 670 K to about 680 K, from about 680 K to about 690 K, from about 690 K to about 700 K, from about 700 K to about 710 K, from about 710 K to about 720 K, from about 720 K to about 730 K, from about 730 K to about 740 K, from about 740 K to about 750 K, from about 750 K to about 760 K, from about 760 K to about 770 K, from about 770 K to about 780 K, from about 780 K to about 790 K, from about 790 K to about 800 K, from about 800 K to about 810 K, from about 810 K to about 820 K, from about 820 K to about 830 K, from about 830 K to about 840 K, from about 840 K to about 850 K, from about 850 K to about 860 K, from about 860 K to about 870 K, from about 870 K to about 880 K, from about 880 K to about 890 K, from about 890 K to about 900 K.

[0157]

[0103] In some embodiments, heating occurs for about 30 minutes to about 4 hours. In some embodiments, heating occurs for about 30 minutes to about 1 hour. In some embodiments, heating occurs for about 1 hour to about 2 hours. In some embodiments, heating occurs for about 2 hours to about 3 hours. In some embodiments, heating occurs for about 3 hours to about 4 hours. In some embodiments, heating occurs for about 30 minutes, about 1 hour, about 1.5 hours, about 2 hours, about 2.5 hours, about 3 hours, about 3.5 hours, or about 4 hours.

[0158]

[0104] In some embodiments, heating occurs at a temperature between 500 and 2500 K. In some embodiments, heating occurs at a temperature between 500 and 2000 K. In some embodiments, heating occurs at a temperature between 500 and 1500 K. In some embodiments, heating occurs at a temperature between 750 and 1250 K. In some embodiments, heating occurs in a gas atmosphere. In some embodiments, the gas atmosphere comprises air, oxygen, nitrogen, or a combination thereof. In some embodiments, the gas atmosphere is substantially free of oxygen. In some embodiments, heating removes a volatile component. In some embodiments, heatingAttorney Docket No.: 733PCT601

[0159] occurs in a muffle furnace, a rotary furnace, a batch furnace, a continuous furnace, or a combination thereof. In some embodiments, heating occurs in an indirect-heated rotary calciner. In some embodiments, the indirect-heated rotary calciner is a batch or continuous calciner. In some embodiments, the indirect-heated rotary calciner is configured to operate in batch mode. In some embodiments, the indirect-heated rotary calciner is configured to operate in continuous mode. In some embodiments, the indirect-heated rotary calciner comprises a countercurrent flow of dehumidified air. A countercurrent flow of dehumidified air, according to some embodiments, can reduce the impact of humidity on sintering within the lithium-selective ion exchange during heating. In some embodiments, the indirect-heated rotary calciner comprises a countercurrent flow of low pressure steam. A countercurrent flow of low pressure steam, according to some embodiments, can reduce the surface area of the lithium-selective ion exchange without increasing the temperature of the calciner. In some embodiments, the indirect-heated rotary calciner comprises lifter internals. In some embodiments, heating occurs on heated vibrating conveyors. In some embodiments, heating solidifies the one or more binders to form the lithiumselective ion exchange. In some embodiments, heating further comprises a pre-heating step. In some embodiments, the pre-heating step reduces the moisture content of the pre-calcined lithium-selective ion exchange. In some embodiments, the pre-heating step is used in conjunction with an indirect-heated rotary calciner that is configured to operate in continuous mode.

[0160]

[0105] In some embodiments, the lithium-selective ion exchange provided following heating is used for lithium extraction according to any embodiment of a method or system for lithium extraction (e.g., from a liquid resource) as described herein, including in sections “Process of extracting lithium from a liquid resource” and “Devices and vessels for beds of an ion exchange material.” The utility of the lithium-selective ion exchange materials provided herein is not limited to use according to the embodiments of methods and systems for lithium extraction described herein, particularly in view of the advantageous properties of such lithium-selective ion exchange materials that are expounded throughout the present disclosure.

[0161]

[0106] In some embodiments, heating occurs within a pusher kiln, a roller hearth kiln, a rotary kiln, a rotary furnace, a muffle furnace, a batch furnace, or a continuous furnace. In some embodiments, heating is conducted using electrical power to minimize contamination by combustion fuel by-products. In some embodiments, heating is conducted via radiative heating, convective heating, microwave heating, or combinations thereof. In some embodiments heating is conducted by indirectly -fired furnaces or kilns to minimize contamination by combustion byproducts. In some embodiments, heating is conducted by directly-fired furnaces or kilns. InAttorney Docket No.: 733PCT601

[0162] some embodiments, direct-firing utilizes fuels comprising natural gas, propane, syngas, carbon monoxide, hydrogen, or combinations thereof. In some embodiments, direct-firing operates in a fuel-rich or fuel-lean regime to control oxidation state of the product mixed metal oxide.

[0163]

[0107] In some embodiments, the heating step occurs in an indirect-heated rotary calciner. In some embodiments, the indirect-heated rotary calciner is a batch or continuous calciner. In some embodiments, the indirect-heated rotary calciner is configured to operate in batch mode. In some embodiments, the indirect-heated rotary calciner is configured to operate in continuous mode. In some embodiments, the indirect-heated rotary calciner comprises a countercurrent flow of dehumidified air. A countercurrent flow of dehumidified air, according to some embodiments, can reduce the impact of humidity on sintering within the mixed metal oxide product during heating. In some embodiments, the indirect-heated rotary calciner comprises a countercurrent flow of low-pressure steam. In some embodiments, the indirect-heated rotary calciner comprises lifter internals. In some embodiments, heating the mixture of lithium salt precursor and metal precursor occurs on heated vibrating conveyors.

[0164]

[0108] In some embodiments, the loaded bed height of the ceramic saggars used to contain the mixture of precursors during the heating step is controlled to maximize uniformity of the reaction, increase uniformity of the mixed metal oxide stoichiometry, allow by-product gas release, reduce amount of residual unreacted precursors, or combinations thereof. In some embodiments, the loaded bed height of the mixture of precursors in the ceramic saggars is limited to about 2 to 5 cm. In some embodiments, the loaded bed height of the mixture of precursors in the ceramic saggars is limited to about 5 to 10 cm. In some embodiments, the loaded bed height of the mixture of precursors in the ceramic saggars is limited to about 10 to 15 cm. In some embodiments, the loaded bed height of the mixture of precursors in the ceramic saggars is limited to about 1 to 2 cm, 2 to 4 cm, 4 to 6 cm, 6 to 8 cm, 8 to 10 cm, 10 to 12 cm, or 12 to 15 cm.

[0165]

[0109] In some embodiments, a rotary kiln or furnace is used to mix precursors more uniformly during the heating process. In some embodiments, knockers are used on the rotary kiln or furnace during the heating process to reduce build-up of static solid materials within the heating vessel. In some embodiments, rotation speed of the rotary kiln is controlled to optimize mixing of the precursors, reaction rate, dust generation, or combinations thereof. In some embodiments, milling media is added to the mixture of precursors during the heating step in a rotary kiln or furnace to encourage more uniform mixing and reaction. In some embodiments, milling media is utilized during the heating step in a rotary kiln or furnace to reduce the size of the mixed metal oxide product within the same unit operation.Attorney Docket No.: 733PCT601

[0166]

[0110] In some embodiments, heating occurs within a controlled gas atmosphere supplied by fresh gas comprising air, oxygen, nitrogen, or combinations thereof. In some embodiments, the level of oxygen in the supply of fresh gas is controlled to maintain the correct oxidation state of the cations in the mixed metal oxide. In some embodiments, the supply of fresh gas has oxygen levels ranging from about 0 to 20 volume percent. In some embodiments, the supply of fresh gas has oxygen levels ranging from about 20 to 40 volume percent. In some embodiments, the supply of fresh gas has oxygen levels ranging from about 40 to 60 volume percent. In some embodiments, the supply of fresh gas has oxygen levels ranging from about 60 to 80 volume percent. In some embodiments, the supply of fresh gas has oxygen levels ranging from about 80 to 100 volume percent. In some embodiments, the supply of fresh gas is controlled to reduce moisture content. In some embodiments, the dew point of the supply of fresh gas is controlled to about -40 to -70 °C. In some embodiments, the dew point of the supply of fresh gas is controlled to about -10 to -40 °C. In some embodiments, the dew point of the supply of fresh gas is controlled to about 0 to -20 °C.

[0167]

[0111] In some embodiments, the supplied gas into the heating chamber is pre-heated to the target temperature of the mixture of lithium salt precursor and metal precursor. In some embodiments, the supplied gas into the heating chamber is directed through antechambers or piping contained within the furnace or kiln to pre-heat the gas. In some embodiments, the supplied gas is fed at ambient external temperatures and allowed to heat up upon entry to the heating chamber.

[0168]

[0112] In some embodiments, the exchange rate of fresh gas into the controlled atmosphere of the heating step is controlled to control reaction rate, heating rate of the mixture, by-product gas concentration in the controlled atmosphere and exhaust stream, or combinations thereof. In some embodiments, the controlled gas atmosphere of the heating step has a fresh gas exchange rate of about 5 to 50 vessel volumes per hour. In some embodiments, the controlled gas atmosphere of the heating step has a fresh gas exchange rate of about 50 to 100 vessel volumes per hour. In some embodiments, the controlled gas atmosphere of the heating step has a fresh gas exchange rate of about 100 to 150 vessel volumes per hour. In some embodiments, the controlled gas atmosphere of the heating step has a fresh gas exchange rate of about 1 to 5 vessel volumes per hour, 5 to 10 vessel volumes per hour, 10 to 20 vessel volumes per hour, 20 to 30 vessel volumes per hour, 30 to 40 vessel volumes per hour, 40 to 50 vessel volumes per hour, 50 to 60 vessel volumes per hour, 60 to 70 vessel volumes per hour, 70 to 80 vessel volumes per hour, 80 to 90 vessel volumes per hour, 90 to 100 vessel volumes per hour, 100 to 110 vessel volumes perAttorney Docket No.: 733PCT601

[0169] hour, 110 to 120 vessel volumes per hour, 120 to 130 vessel volumes per hour, 130 to 140 vessel volumes per hour, or 140 to 150 vessel volumes per hour.

[0170]

[0113] In any of the embodiments described herein, the size of the particles of the lithium salt precursor(s), metal precursor(s), synthesis mixture(s), resulting mixed metal oxide(s), or a combination thereof is controlled by sizing or classifying said particles. Systems, methods, and compositions resulting from said classification are described in “Control of the particle size of the metal precursor, lithium salt precursor, mixed metal oxide, or lithium-selective ion exchange material.” It shall be understood that the compositions resulting from, and the methods for, heating mixtures to form a mixed metal oxide as described herein shall equally apply to compositions and methods involving lithium salt precursors, metal precursors, synthesis mixtures, or mixed metal oxides, wherein the particle size is classified or otherwise controlled.

[0171] Absorption of by-product gases

[0172]

[0114] In an aspect of the disclosure, said heating of a mixture of one or more lithium salt precursor(s) and one or more metal precursor(s) generates a by-product gas. In some embodiments, said by-product gas is generated by the decomposition of one or more lithium salt precursor(s), one or more metal precursor(s), or any combination thereof. In some embodiments, simultaneous to the decomposition of one or all of the precursors is a reaction that forms the target product mixed metal oxide

[0173]

[0115] In some embodiments, said by-product gas is generated by the decomposition of one or more chemicals that are added to the mixture to facilitate the reaction between the one or more lithium salt precursor(s) and the one or more metal precursor(s). In some embodiments, said byproduct gas is generated by the decomposition of one or more liquid(s) that are added to the mixture to facilitate the reaction between the one or more lithium salt precursor(s) and the one or more metal precursor(s). In some embodiments, simultaneous to the decomposition of one or all of the precursors, chemicals, and / or liquids, is a reaction that forms the target product mixed metal oxide. Simultaneous to the decomposition of one or all of the precursors is a reaction that forms the target product mixed metal oxide.

[0174]

[0116] In some embodiments, the by-product gas comprises NOX, SOX, CO2, H2O, O2, or combinations thereof. In some embodiments, the by-product gas comprises NOXwherein the lithium salt precursor, metal precursor, or combinations thereof contain nitrates. In some embodiments, the by-product gas comprises NOXwherein the lithium salt precursor comprises lithium nitrate and releases the by-product gas upon decomposition. In some embodiments, the by-product gas comprises NOXwherein the metal precursor comprises manganese nitrate andAttorney Docket No.: 733PCT601

[0175] releases the by-product gas upon decomposition. In some embodiments, the by-product gas comprises NOXwherein the metal precursor comprises ferrous nitrate and releases the byproduct gas upon decomposition. In some embodiments, the by-product gas comprises SOXwherein the lithium salt precursor, metal precursor, or combinations thereof contain sulfates. In some embodiments, the by-product gas comprises SOXwherein the lithium salt precursor comprises lithium sulfate and releases the by-product gas upon decomposition. In some embodiments, the by-product gas comprises SOXwherein the metal precursor comprises manganese sulfate and releases the by-product gas upon decomposition. In some embodiments, the by-product gas comprises SOXwherein the metal precursor comprises ferrous sulfate and releases the by-product gas upon decomposition. In some embodiments, the by-product gas comprises COXwherein the lithium salt precursor, metal precursor, or combinations thereof contain carbonates. In some embodiments, the by-product gas comprises COXwherein the lithium salt precursor comprises lithium carbonate and releases the by-product gas upon decomposition. In some embodiments, the by-product gas comprises COXwherein the metal precursor comprises manganese carbonate and releases the by-product gas upon decomposition. In some embodiments, the by-product gas comprises COXwherein the metal precursor comprises ferrous carbonate and releases the by-product gas upon decomposition.

[0176]

[0117] While by-product gases can be removed and recovered through a variety of industrial processes, the absorbed species are typically discarded as waste, in part because the absorbed gas solution contains impurities.

[0177]

[0118] In one embodiment of an existing system, for example, a solution of nitric acid and hydrogen peroxide is used to absorb nitrogen oxide by-product gases (NOx) into an aqueous solution to form a more concentrated nitric acid solution. The resulting solution has some value when purified and concentrated for sale or use in separate applications. However, this use does not capture the greater value embodied in reusing the nitric acid to produce a high-value lithium salt precursor. In another embodiment of an existing system, for example, a solution of NaOH is used to absorb nitrogen oxide by-product gases (NOx) into an aqueous solution, to form a mixture of sodium nitrate and sodium nitrite. However, the resulting solution contains a mixture of nitrate and nitrite salts, which preclude their use for production of lithium-selective ion exchange materials, which typically require pure compounds. Further, sodium salts are typically inexpensive, rendering it uneconomical to use these salts to produce lithium-selective ion exchange materials.

[0178]

[0119] In an aspect of the disclosure described herein, methods and systems are configured to recover the by-product gases in a manner that produces a pure compound, which can be recycledAttorney Docket No.: 733PCT601

[0179] and reused in the production of lithium-selective ion exchange materials. In one embodiment, the absorbing solution comprises an acidic solution containing the anions of the lithium salt precursors, with absorption of the by-product gas providing additional acid and corresponding anions. In another embodiment, the absorbing solution comprises the cation of the lithium salt precursor, and the gas is absorbed to provide the anion of the lithium salt precursor. In one nonlimiting embodiment, the absorbing solution comprises lithium hydroxide, and the anion is provided by absorbing NOx gases produced by the decomposition of metal salt and metal precursors during the production of lithium-selective ion exchange materials. In a further nonlimiting embodiment, the absorbing solution comprises oxidizing species that convert a mixture of nitrates and nitrites into a pure solution of nitrate. In a further nonlimiting embodiment, the absorbing solution comprises oxidizing species that ensure oxidation of NOx into a pure solution of nitrate. In one embodiment, the oxidizing species is hydrogen peroxide.

[0180]

[0120] The embodiments described above for the case of nitrogen oxides (NOx) are nonlimiting, and are generally applicable to other volatile oxide by-product gases. In some embodiments, these volatile oxide by-product gases comprise sulfur oxides (SOx). In some embodiments, these volatile oxide by-product gases comprise carbon oxides (COx).

[0181]

[0121] For example, a solution of sulfuric acid and hydrogen peroxide can be used to absorb sulfur oxide by-product gases (SOx) into an aqueous solution to form a more concentrated sulfuric acid solution. The resulting solution has some value when purified and concentrated for sale or use in separate applications. However, this use does not capture the greater value embodied in reusing the sulfuric acid to produce a high-value lithium salt precursor. In another embodiment of an existing system, for example, a solution of NaOH is used to absorb sulfur oxide by-product gases (SOx) into an aqueous solution, to form a mixture of sodium sulfite and sodium sulfate. However, the resulting solution contains a mixture of sulfite and sulfate salts, which preclude their use for production of lithium-selective ion exchange materials, which typically require pure compounds. In aspects of the disclosure described herein, methods and systems are configured to recover the by-product gases in a manner that produces a pure compound, which can be recycled and reused in the production of lithium-selective ion exchange materials. In one nonlimiting embodiment, the absorbing solution comprises lithium hydroxide, and the anion is provided by absorbing SOx gases produced by the decomposition of metal salt and metal precursors during the production of lithium-selective ion exchange materials. In a further nonlimiting embodiment, the absorbing solution comprises oxidizing species that convert a mixture of sulfates and sulfites into a pure solution of sulfate. In a further nonlimiting embodiment, the absorbing solution comprises oxidizing species that ensureAttorney Docket No.: 733PCT601

[0182] oxidation of SOx into a pure solution of sulfate (SO42-). In one embodiment, the oxidizing species is hydrogen peroxide.

[0183]

[0122] In an aspect of the disclosure, by-product gases are converted and absorbed by an absorber liquid to form an absorbed gas solution. This absorption allows for recovery of the byproduct gases for further treatment and conversion to a reagent precursor for reuse in the overall system. Simultaneously, by-product gases may be regulated as air pollutants and may require emissions mitigation systems. Absorption of the by-product gases into an absorber liquid serves the dual function of recovering reagents for reuse and reducing air pollutant emissions.

[0184]

[0123] In an aspect of the disclosure described herein, methods and systems are configured to recover the by-product gases in a manner that produces a pure compound, which can be recycled and reused in the production of a mixed metal oxide. In one embodiment, the absorbing solution comprises the cation of the lithium salt precursor, and the gas is absorbed to provide the anion of the lithium salt precursor. In one nonlimiting embodiment, the absorbing solution comprises lithium hydroxide, and the anion is provided by absorbing NOXgases produced by the decomposition of metal salt and metal precursors during the production a mixed metal oxide comprising lithium. In a further nonlimiting embodiment, the absorbing solution comprises oxidizing species that convert a mixture of nitrates and nitrites into a pure solution of nitrate. In one embodiment, the oxidizing species is hydrogen peroxide. In some embodiments, the mixed metal oxide comprising lithium is a lithium-selective ion exchange material.

[0185]

[0124] In some embodiments, the by-product gases comprise NOX, the one or more absorbers contain an alkaline aqueous solution comprising lithium hydroxide, and the oxidizing agent contain one of the said one or more absorbers comprises hydrogen peroxide. In some embodiments, one or more of the following chemical reactions occur in said aqueous solution, wherein all reactions occur should be understood to represent an equilibrium state of chemical species. In some embodiments, the ultimate result of the reactions is the production or a lithium salt precursor. In some embodiments, said lithium salt precursor is lithium nitrate.

[0186] N2O4 (aq)+H2O - HNO2 + HNO3

[0187] NO2 (aq)+H2O HNO2+ HNO3

[0188] N2O3 (aq)+H2O —2 HNO2

[0189] LiOH (aq) + HNO2LiNO2+ H2O

[0190] LiOH (aq)+ HNO3LiNO3+ H2O

[0191] LiNO2(aq) + H2O2LiNO3+ H2O

[0192] LiOH (aq) + HNO3 (aq) LiNO3(aq) + H2O

[0193] LiNO2(aq) + 2 HNO3(aq) 2NO2(g) + LiNO3+H2OAttorney Docket No.: 733PCT601

[0194] 2LiNO2(aq) + 2HNO3(aq) 2LiNO3+ NO2(g) +NO (g) + H2O

[0195]

[0125] In some embodiments, the by-product gases comprise SOX, the one or more absorbers contain an alkaline aqueous solution comprising lithium hydroxide, and the oxidizing agent contain one of the said one or more absorbers comprises hydrogen peroxide. In some embodiments, one or more of the following chemical reactions occur in said aqueous solution, wherein all reactions occur should be understood to represent an equilibrium state of chemical species. In some embodiments, the ultimate result of the reactions is the production or a lithium salt precursor. In some embodiments, said lithium salt precursor is lithium sulfate.

[0196] SO3(aq)+H2O H2SO4

[0197] SO2(aq)+H2O H2SO3

[0198] 2 LiOH (aq) + H2SO3Li2SO3+ 2 H2O

[0199] 2 LiOH (aq)+ H2SO4Li2SO4+ 2 H2O

[0200] Li2SO3(aq) + H2O2Li2SO4+ H2O

[0201]

[0126] In an aspect of this system, the solution produced from absorption of by-product gases by an absorber solution is described as an absorbed gas solution. In some embodiments, the absorbed gas solution is transferred from the absorber system to a separate conversion system for further treatment to produce a lithium salt precursor or a metal precursor.

[0202]

[0127] In some embodiments, lithium carbonate, lithium hydroxide, or combinations thereof are added to the absorbed gas solution to neutralize acids present and convert the solution to a lithium salt precursor solution. Herein, the molar ratio (atomic lithium basis) of combinations of lithium carbonate (Li2CO3) and lithium hydroxide (LiOH) refers to the ratio of moles of lithium derived from lithium carbonate to the moles of lithium derived from lithium hydroxide. For example, one mole of lithium carbonate mixed with one mole of lithium hydroxide would result in a molar ratio (atomic lithium basis) of lithium carbonate and lithium hydroxide of 2: 1. In some embodiments, the molar ratio (atomic lithium basis) of lithium carbonate to lithium hydroxide added the absorbed gas solution ranges from about 90:10 to 97:3. In some embodiments, the molar ratio (atomic lithium basis) of lithium carbonate to lithium hydroxide added the absorbed gas solution ranges from about 10:90 to 90:10. In some embodiments, the molar ratio (atomic lithium basis) of lithium carbonate to lithium hydroxide added the absorbed gas solution ranges from about 0:100 to 10:90. In some embodiments, the molar ratio (atomic lithium basis) of lithium carbonate to lithium hydroxide added the absorbed gas solution ranges from about 0:100 to 5:95, 5:95 to 10:90, 10:90 to 15:85, 15:85 to 20:80, 20:80 to 25:75, 25:75 toAttorney Docket No.: 733PCT601

[0203] 30:70, 30:70 to 35:65, 35:65 to 40:60, 40:60 to 45:55, 45:55 to 50:50, 50:50 to 55:45, 55:45 to 60:40, 60:40 to 65:35, 65:35 to 70:30, 70:30 to 75:25, 75:25 to 80:20, 80:20 to 85:15, 85:15 to 90:10, 90: 10 to 95:5, or 95:5 to 100:0.

[0204]

[0128] In embodiments where lithium carbonate is added to neutralize acids present, carbon dioxide is produced. In some embodiments, said carbon dioxide bubbles out of the neutralized solution. In some embodiments, it is preferable to maximize usage of lithium carbonate over lithium hydroxide due to lower health hazards, lower reagent cost, increased shelf stability, or combinations thereof. In some embodiments, it is preferable to maximize usage of lithium hydroxide due to simpler reaction dynamics (e.g. no off-gassing, foaming, or pH buffering), reduced formation of dissolved carbonate and bicarbonate species, reduced carbonate scaling, or combinations thereof. In some embodiments, a combination of lithium carbonate and lithium hydroxide is used to take advantage of a mix of the aforementioned advantages. In some embodiments, lithium carbonate is added to the absorbed gas solution until a pH of about 0.5-1 is achieved, and lithium hydroxide is added to further increase the pH of the solution to a final pH of about 7, 8, 9, 10 or 11. In some embodiments, lithium hydroxide is added as an aqueous solution, a solid powder, or combinations thereof.

[0205]

[0129] In some embodiments, sodium bicarbonate, sodium carbonate, sodium hydroxide, or combinations thereof are added to the absorbed gas solution to neutralize acids present and convert the solution to a lithium salt precursor solution. In some embodiments, manganese hydroxide, manganese carbonate, manganese ore, or combinations thereof are added to the absorbed gas solution to neutralize acids present and convert the solution to a metal precursor solution. In some embodiments, ferrous hydroxide, ferrous carbonate, metallic iron, or combinations thereof are added to the absorbed gas solution to neutralize acids present and convert the solution to a metal precursor solution. In some embodiments, the temp

[0206]

[0130] In some embodiments, the absorbed gas solution may contain undesirable impurities. In some embodiments, the impurities comprise solid particulates, dissolved calcium, dissolved magnesium, dissolved transition metal species, or combinations thereof. In some embodiments, the dissolved transition metal species comprise iron, manganese, titanium, nickel, cobalt, copper, chromium, or combinations thereof. In some embodiments, the undesired impurities are removed with hydrometallurgical processes, filtration, ion-exchange, adsorption, membrane filtration, or combinations thereof. In some embodiments, dissolved impurities are precipitated by increasing the pH of the absorbed gas solution. In some embodiments, this increase in pH is achieved with the addition of lithium carbonate, lithium hydroxide, or combinations thereof. In some embodiments, this increase in pH is achieved with the addition of sodium bicarbonate,Attorney Docket No.: 733PCT601

[0207] sodium carbonate, sodium hydroxide, or combinations thereof. In some embodiments, oxidants are introduced to the absorbed gas solution to oxidize dissolved transition metal species in the solution and facilitate oxidation.

[0208]

[0131] In some embodiments, the converted absorbed gas solution is filtered to remove residual solids and precipitates prior to further processing. In some embodiments, filtration occurs in a filtration system comprising a bag filter, a candle filter, a cartridge filter, a media filter, a depth filter, a sand filter, a membrane filter, an ultrafiltration system, a microfiltration filter, a nanofiltration filter, a cross-flow filter, a dead-end filter, a drum filter, a filter press, or a combination thereof. In some embodiments, residual solids and precipitates are separated from the converted absorbed gas solution by sedimentation, centrifugation, thickening, flocculation, coagulation, or combinations thereof.

[0209]

[0132] An aspect of the disclosure is the full integrated process that produces a mixed metal oxide through a heat treatment of a mixture of a lithium salt precursor and metal precursor, releases by-product gases that are absorbed and converted back to the lithium salt precursor or metal precursor with minimal loss of the by-product gas.

[0210] Control of the particle size of the metal precursor, lithium salt precursor, mixed metal oxide, or lithium-selective ion exchange material

[0211]

[0133] An aspect of the invention disclosed herein is controlling the size of particles of the lithium-selective ion exchange material. An aspect of the invention disclosed herein is controlling the size of particles of the mixed metal oxide. An aspect of the invention disclosed herein a lithium-selective ion exchange material comprising particles of the mixed metal oxide whose size has thus been controlled. An aspect of the invention disclosed herein is controlling the size of particles of the metal precursor, lithium salt precursor, or both which are used in manufacturing the mixed metal oxide. An aspect of the invention disclosed herein is controlling the size of particles of a mixed metal oxide used in manufacturing a lithium-selective ion exchange material. An aspect of the invention disclosed herein is controlling the size of particles of a spent lithium-selective ion exchange material before it is recycled.

[0212]

[0134] In some embodiments, said controlling of the size of the particles of the lithium-selective ion exchange material, metal precursor, lithium salt precursor, or mixed metal oxide yield materials with optimal properties for lithium extraction. In some embodiments, said optimal properties include physicochemical, textural, and hydrodynamic properties of the material, including, but not limited to: specific surface area (including as measured by the BET method from N2 physisorption), porosity, specific pore volume (including as measured by N2Attorney Docket No.: 733PCT601

[0213] physisorption), particle size distribution (including dlO and d90 values), pore size distribution (including pore dlO and d90values), the pressure drop through a packed bed of said material, settling velocity, and lithium extraction properties. Exemplary embodiment and values of said properties, and methods and systems for achieving said properties, are included in Table 1 and associated examples.

[0214]

[0135] In some embodiments, said optimal properties result in improved or optimized performance parameters for lithium recovery. In some embodiments, improved or optimized performance parameters comprise a longer useful lifetime of the ion exchange material used in the methods and systems described herein. In some embodiments, improved or optimized performance parameters comprise a higher lithium production rate for flow of the same amount of liquid resource across the ion exchange material used in the methods and systems described herein. In some embodiments, improved or optimized performance parameters comprise a higher lithium purity of the lithium provided by the ion exchange material used in the methods and systems described herein. In some embodiments, improved or optimized performance parameters comprise a greater quantity of lithium provided by a given quantity of ion exchange material over its useful lifetime when the ion exchange material is used according to the methods and systems described herein. In some embodiments, improved or optimized performance parameters comprise an increase in overall lithium recovery.

[0215]

[0136] In an aspect, the size of the particles metal precursor used in the preparation, synthesis, of manufacturing of said ion exchange material is controlled, to affect the final size of the particles of the lithium-selective ion exchange material. In an aspect, the size of the particles of the lithium salt precursor used in the preparation, synthesis, of manufacturing of said ion exchange material is controlled, to affect the final size of the particles of the lithium-selective ion exchange material.

[0216]

[0137] In an aspect, a lithium salt precursor is contacted with a metal precursor to generate a synthesis mixture, and the size of said synthesis mixtures is controlled, prior to the preparation, synthesis, of manufacturing of the ion exchange material therefrom, to affect the final size of the particles of the lithium-selective ion exchange material.

[0217]

[0138] In an aspect, the particles of the mixed metal oxide are at least partially coated by, embedded in, adhered to, or otherwise supported by one or more matrix materials. In an aspect, the size of the particles of the mixed metal oxide used in the preparation, synthesis, of manufacturing of said ion exchange material is controlled, to affect the final size of the particles of the lithium-selective ion exchange material. In an aspect, the size of the particles of the matrix material used in the preparation, synthesis, of manufacturing of said ion exchange material isAttorney Docket No.: 733PCT601

[0218] controlled, to affect the final size of the particles of the lithium-selective ion exchange material. In an aspect, the size of the particles of the matrix material and the mixed metal oxide used in the preparation, synthesis, of manufacturing of said ion exchange material is controlled, to affect the final size of the particles of the lithium-selective ion exchange material.

[0219]

[0139] In an aspect, the mixed metal oxide is embedded in, adhered to, or otherwise supported by a first matrix material, and further embedded in, adhered to, or otherwise supported in a second matrix material to form the final lithium-selective ion exchange material. In some embodiments, the size of the particles of the mixed metal oxide, the first matrix material, the mixed metal oxide embedded in the first matrix material, the second matrix material, or the resulting lithium-selective ion exchange material is controlled. In some embodiments, three or more matrix materials are used to yield the final lithium-selective ion exchange material, and the size of any component forming said material is controlled.

[0220]

[0140] In an aspect, the size of the particles of the final lithium-selective ion exchange material is controlled. In some embodiments, the size of the particles of lithium salt precursor, metal precursor, the matrix material, any synthesis intermediates, or the final lithium-selective ion exchange material are optionally controlled to yield the final lithium-selective ion exchange material.

[0221]

[0141] In some embodiments, the size of the particles is controlled to yield particles with specific particle size distributions, as characterized by the dl, d5, dlO, d90, d95, and d99 of the particles. For example, controlling the particle size from dlO to d90 would yield a range where 80% of the particles are within that range. It should be understood that the size of the particles described below can apply to the lithium-selective ion exchange material, or to any components thereof whose size was controlled in the synthesis of said materials, including but not limited to the lithium salt precursor, the metal precursor, the mixed metal oxide, the synthesis mixture, the matrix material, any intermediate materials thereof, or any combinations hereof.

[0222]

[0142] In some embodiments, the size of the particles is controlled such that the d10is in the range of from about 10 nm to about 5 mm. In some preferred embodiments, the size of the particles is controlled such that the d10is in the range of from about 0.1 to about 500 μm. In yet more preferred embodiments, the size of the particles is controlled such that the d10is in the range of from about 1 to about 250 μm.

[0223]

[0143] In some embodiments, the size of the particles is controlled such that the dlO is in the range of from about 0.1 to about 500 pm. In some embodiments, the size of the particles is controlled such that the dio of the particles are selected to from the following values: about 0.1Attorney Docket No.: 733PCT601

[0224] pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 jam, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 jam.

[0225]

[0144] In some embodiments, the size of the particles is controlled such that the d90 is in the range of from about 0.1 to about 500 µm. In some embodiments, the d90 of the particles are selected to from the following values: about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm.

[0226]

[0145] In some embodiments, the size of the particles is controlled such that the d5 is in the range of from about 0.1 to about 500 µm. In some embodiments, the d5 of the particles are selected to from the following values: about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm.

[0227]

[0146] In some embodiments, the size of the particles is controlled such that the d95 is in the range of from about 0.1 to about 500 pm. In some embodiments, the d95 of the particles are selected to from the following values: about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 urn.

[0228]

[0147] In some embodiments, the size of the particles is controlled such that the d1 is in the range of from about 0.1 to about 500 µm. In some embodiments, the d1 the particles are selected to from the following values: about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm.

[0229]

[0148] In some embodiments, the size of the particles is controlled such that the d99 is in the range of from about 0.1 to about 500 µm. In some embodiments, the d99 the particles are selected to from the following values: about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm.

[0230]

[0149] In an aspect, the size of the particles is controlled by processing the particles through a size classification unit. In some embodiments, the size classification units are designed to retain particles above a cutoff minimum size while allowing smaller particles to pass through. In some embodiments, the cutoff size for the sieving process can be selected from a range of values, including from about 0.1 um to about 0.5 pm, from about 1 um to about 5 pm, from about 10 um to about 25 pm, from about 50 um to about 75 pm, from about 100 um to about 250 pm, and from about 500 pm. The choice of cutoff size depends on the desired particle size distribution and the specific application of the lithium-selective ion exchange material. In someAttorney Docket No.: 733PCT601

[0231] embodiments, the smaller particles that are not retained by the classification device comprise about 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 75%, 90% or 99% of particles of the material before classification.

[0232]

[0150] In some embodiments, said size classification unit comprises on or more: dry screening, air classification, wet classification, decantation, sieving, screening, sifting, gravity separation, elutriation, centrifugation, settling, clarification, filtering, magnetic separation, electrostatic separation, flotation, and hydrometallurgical separation processes, or combined processes thereof.

[0233]

[0151] In some embodiments, said dry screening comprises one or more sieves, including but not limited to vibratory sieves, high-energy sifters, jet sieves, tumbling sieves, or other sieving devices. These devices are designed to retain particles above a minimum size while allowing smaller particles to pass through. In some embodiments, the dry screening process utilizes mechanical vibration devices, rotary or linear screens to enhance the efficiency of particle separation. In some embodiments, the cutoff size for the sieving process can be selected from a range of values, including from about 0.1 um to about 0.5 pm, from about 1 um to about 5 pm, from about 10 um to about 25 pm, from about 50 um to about 75 pm, from about 100 um to about 250 pm, and from about 500 pm. The choice of cutoff size depends on the desired particle size distribution and the specific application of the lithium-selective ion exchange material.

[0234]

[0152] In some embodiments, said air classification comprises one or more devices selected from: gravitational air classifiers, gravitational inertial air classifiers, centrifugal air classifiers, gyrotor air classifiers, cyclones, or combinations thereof. These devices operate by using airflow to separate particles based on their size, shape, and density, allowing for precise control over the particle size distribution. In some embodiments, the cutoff size for the air classification process can be selected from a range of values, including from about 0.1 um to about 0.5 pm, from about 1 um to about 5 pm, from about 10 um to about 25 pm, from about 50 um to about 75 pm, from about 100 um to about 250 pm, and from about 500 pm. The choice of method cutoff size depends on the desired particle size distribution and the specific application of the lithiumselective ion exchange material.

[0235]

[0153] In some embodiments, the wet classification unit comprises one or more devices selected from: a clarifier, a lamellar clarifier, hydrocyclone, a cyclone, an elutriation device, a reflux classifier, a wet sieve, a wet screening device, a vibratory wet screening device, a decantation device, or combinations thereof. These devices operate by using various principles such as gravity, centrifugal force, and mechanical vibration to separate particles based on their size, shape, and density. In some embodiments, the wet classification process is enhanced byAttorney Docket No.: 733PCT601

[0236] incorporating mechanical vibration devices or flow distribution devices to improve the efficiency of particle separation. In some embodiments, the wet classification device comprises one or more spraying devices designed to wash the particles, one or more mechanical vibration devices designed to allow efficient washing of the particles, one or more flow distribution devices configured to efficiently direct the particles into the one or more screens or mechanical components of the device. In some embodiments, the cutoff size for the wet classification process can be selected from a range of values, including from about 0.1 um to about 0.5 pm, from about 1 um to about 5 pm, from about 10 um to about 25 pm, from about 50 um to about 75 pm, from about 100 um to about 250 pm, and from about 500 pm. The choice of method cutoff size depends on the desired particle size distribution and the specific application of the lithium-selective ion exchange material.

[0237]

[0154] In some embodiments, the wet classification further comprises a repulping unit configured to suspend the particles prior to processing of the particles through the wet classification unit. The repulping unit may include various devices, such as agitators, mixers, or stirrers, designed to efficiently re-suspend solid particles in a liquid medium. The unit is designed so that particles are uniformly distributed within the liquid, preventing sedimentation and facilitating an even flow through subsequent classification stages. In some embodiments, some repulping units may incorporate internal structures, such as baffles and lamella, or external components, such as ultrasonic or mechanical vibration elements, to enhance particle suspension.

[0238]

[0155] In some embodiments of the wet classification device, water used is recycled. In some embodiments, particles are separated from the water before recycling of water. In some embodiments, said separation is performed by a filtration device. In some embodiments, filtration devices generally consist of a porous medium that allows liquid to pass through while retaining solid particles. In some embodiments, these devices can include filter presses, membrane filters, sand filters, ultrafilters, candle filters, and Nutsche filters, which vary in their mechanisms and the size of particles they capture. In some embodiments, filter aid is used to improve filtration flux, efficiency, or combinations thereof. In some embodiments, this filter aid can include diatomaceous earth, cellulose, perlite, agricultural fibers, saw dust, rice hull ash, paper fibers, or combinations thereof. In some embodiments, solid-separation devices are used to separate solid particles from a mixture or suspension. In some embodiments, these devices can use methods such as centrifugation, which relies on centrifugal force to separate particles based on their density, or sedimentation, which allows particles to settle by gravity in a liquid. In someAttorney Docket No.: 733PCT601

[0239] embodiments, water is recovered using reverse osmosis, which involves forcing water through a semipermeable membrane to remove impurities and reuse the water efficiently.

[0240]

[0156] In some embodiments, the particles that were classified in a wet classification device are dried. In some embodiments, said dried particles are further used in the synthesis of a lithiumselective ion exchange material. For example, a wet classified metal precursor can be then used to prepare a synthesis mixture by contacting a lithium salt to it, and said mixture heated to produce a mixed metal oxide. In some embodiments, said drying is performed in a convection drier, a vacuum drier, or other device designed to remove a liquid from a solid at ambient or elevated temperature. In some embodiments, said drying is performed at temperatures of controlled to be in the range of from about 270 K to about 770 K. In some embodiments, said drying is performed at temperatures of controlled to be in the range of: from about 270 K to about 280 K, from about 280 K to about 290 K, from about 290 K to about 300 K, from about 300 K to about 310 K, from about 310 K to about 320 K, from about 320 K to about 330 K, from about 330 K to about 340 K, from about 340 K to about 350 K, from about 350 K to about 360 K, from about 360 K to about 370 K, from about 370 K to about 380 K, from about 380 K to about 390 K, from about 390 K to about 400 K, from about 400 K to about 410 K, from about 410 K to about 420 K, from about 420 K to about 430 K, from about 430 K to about 440 K, from about 440 K to about 450 K, from about 450 K to about 460 K, from about 460 K to about 470 K, from about 470 K to about 480 K, from about 480 K to about 490 K, from about 490 K to about 500 K, from about 500 K to about 510 K, from about 510 K to about 520 K, from about 520 K to about 530 K, from about 530 K to about 540 K, from about 540 K to about 550 K, from about 550 K to about 560 K, from about 560 K to about 570 K, from about 570 K to about 580 K.

[0241]

[0157] In some embodiments, the air or wet classification device is designed for the efficient liberation of smaller particles. In some embodiments, said small particles are thus separated from the more desirable larger particles. In some embodiments, larger particles have more advantageous properties for lithium extraction, making it desirable to separate these from said small particles. In some embodiments, smaller particles interfere with the operation of lithium extraction system, for example by clogging packed beds or slowly bleeding into process streams, and it is thus desirable to separate these from larger particles. In some embodiments, the efficient liberation of small particles is achieved by a device designed to enhance the washing and classification processes, thereby ensuring optimal particle size distribution. In some embodiments, the system may incorporate one or more spraying or blowing devices that are specifically engineered for this purpose. In some embodiments, mechanical vibration devicesAttorney Docket No.: 733PCT601

[0242] can be utilized to facilitate the efficient separation of small particles from larger particles. In some embodiments, the devices incorporate flow distributors configured to direct the particles efficiently into the screens or other mechanical components of the classification unit. In some embodiments, said components are employed in tandem, thus achieving high efficiency and precision in the liberation and classification of smaller particles, ultimately contributing to achieving of desirable particle compositions.

[0243]

[0158] In an aspect, the metal precursor classified by any of the methods described herein, is used to prepare a synthesis mixture by contacting a lithium salt to it, and said mixture heated to produce a mixed metal oxide. In some embodiments, a lithium-selective ion exchange material comprises particles of said mixed metal oxide. In some embodiments, particles of said mixed metal oxide are further classified, or their size generally controlled, to result in an advantageous particle size, textural, and hydrodynamic properties of the final formulation of lithium-selective ion exchange material.

[0244]

[0159] In an aspect, the lithium salt precursor classified by any of the methods described herein, is used to prepare a synthesis mixture by contacting a lithium salt to it, and said mixture heated to produce a mixed metal oxide. In some embodiments, a lithium-selective ion exchange material comprises particles of said mixed metal oxide. In some embodiments, particles of said mixed metal oxide are further classified, or their size generally controlled, to result in an advantageous particle size, textural, and hydrodynamic properties of the final formulation of lithium-selective ion exchange material.

[0245]

[0160] In some embodiments, the metal precursor and lithium salt precursor are both classified to yield controlled particle sizes that are advantageous for the synthesis of the mixed metal oxide. In some embodiments, the metal precursor particles rejected by the classification unit are recycled to synthesize a metal precursor. In some embodiments, the mixed metal oxide particles rejected by the classification unit are recycled to synthesize a mixed metal oxide or metal precursor. In some embodiments, the lithium-selective ion exchange material particles rejected by the classification unit are recycled to synthesize a mixed metal oxide or metal precursor. In some embodiments, said recycling comprising dissolving or digesting said metal precursor, mixed metal oxide, or lithium-selective ion exchange material in one or more solvent, and then crystallizing a recycling material therefrom.

[0246]

[0161] In some embodiments, the size of the particles of the lithium salt precursor is increased to yield the final lithium salt precursor precursor. In some embodiments, the size of the particles of the lithium salt precursors is decreased to yield the final lithium salt precursor precursor. In some embodiments, the size of the particles of the lithium salt precursors is first increased, thenAttorney Docket No.: 733PCT601

[0247] decreased to yield the final lithium salt precursor precursor. In some embodiments, the size of the particles of the lithium salt precursors is first increased, then decreased and finally classified to yield the final lithium salt precursor precursor. Said classification occurs by any of the methods, devices, and systems described in “Control of the particle size of the metal precursor, lithium salt precursor, mixed metal oxide, lithium salt precursor, or lithium-selective ion exchange material.”

[0248]

[0162] In some embodiments, in the size of the particles of the lithium salt precursor is increased by extrusion, intrusion, casting, pelletizing, tabletizing, pressing, granulating, calendering, compression molding, thermoforming, sintering, dissolving and recrystallizing, precipitation of fresh lithium salt precursor onto existing particles or otherwise treating the particles to form aggregates thereof.

[0249]

[0163] In some embodiments, after the size lithium salt precursor being increased, the size of the particles of the lithium salt precursor is reduced prior to use of said lithium salt precursor to obtain a lithium salt precursor precursor. In some embodiments, the reduction in the size of the particles is reduced by processing said particles of a metal precursor by a method selected from: crushing, grinding, cutting, attrition, milling (including jet milling, cryo milling, ball milling, hammer milling, pin milling, disc milling, roller milling, attrition milling, fluid energy milling, ultrasonic milling, high-shear milling, wet milling, dry milling, bead milling, vibratory milling, planetary ball milling, fluid bed milling, pancake milling, loop milling, ball milling, impact milling, colloid milling, air-jet milling, conical milling), delumping, granulating, self-attrition, shredding, pulverization, micronization, ultrasonic treatment, or other methods of size reduction acting through the forces of impact, shear, compression, combinations, or process integrations thereof.

[0250]

[0164] In some embodiments, the size of the lithium salt precursor particles is controlled such that such that the d10 is in the range of from about 10 nm to about 5 mm. In some preferred embodiments, the size of the particles is controlled such that the d10 is in the range of from about 0.1 to about 500 pm. In yet more preferred embodiments, the size of the particles is controlled such that the d10 is in the range of from about 1 to about 250 pm. In some embodiments, the size of the particles is controlled such that the d10 is in the range of from about 0.1 to about 500 pm. In some embodiments, the size of the particles is controlled such that the d10 of the particles are selected to from the following values: about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 pm. In some embodiments, the size of the particles is controlled such that the d90 is in the range of from about 0.1 to about 500 pm. In some embodiments, the d90 ofAttorney Docket No.: 733PCT601

[0251] the particles are selected to from the following values: about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 pm. In some embodiments, the size of the particles is controlled such that the d5 is in the range of from about 0.1 to about 500 pm. In some embodiments, the d5 of the particles are are selected to from the following values: about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 pm. In some embodiments, the size of the particles is controlled such that the d95 is in the range of from about 0.1 to about 500 µm. In some embodiments, the d95 of the particles are selected to from the following values: about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm. In some embodiments, the size of the particles is controlled such that the d1 is in the range of from about 0.1 to about 500 pm. In some embodiments, the d1 the particles are selected to from the following values: about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 pm. In some embodiments, the size of the particles is controlled such that the d99 is in the range of from about 0.1 to about 500 pm. In some embodiments, the d99 the particles are are selected to from the following values: about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 um.

[0252]

[0165] In some embodiments, the size of the particles of the metal precursor is increased to yield the final metal precursor. In some embodiments, the size of the particles of the metal precursors is decreased to yield the final metal precursor. In some embodiments, the size of the particles of the metal precursors is first increased, then decreased to yield the final metal precursor. In some embodiments, the size of the particles of the metal precursors is first increased, then decreased and finally classified to yield the final metal precursor. Said classification occurs by any of the methods, devices, and systems described in “Control of the particle size of the metal precursor, lithium salt precursor, mixed metal oxide, metal precursor, or lithium-selective ion exchange material.”

[0253]

[0166] In some embodiments, the size of the particles of the metal precursor is increased by extrusion, intrusion, casting, pelletizing, tabletizing, pressing, granulating, calendering, compression molding, thermoforming, sintering, dissolving and recrystallizing, precipitation of fresh metal precursor onto existing particles, combinations thereof, or otherwise treating the particles to form aggregates thereof.

[0254]

[0167] In some embodiments, after the size metal precursor being increased, the size of the particles of the metal precursor is reduced prior to use of said metal precursor to obtain a metalAttorney Docket No.: 733PCT601

[0255] precursor. In some embodiments, the reduction in the size of the particles is reduced by processing said particles of a metal precursor by a method selected from: crushing, grinding, cutting, attrition, milling (including jet milling, cryo milling, ball milling, hammer milling, pin milling, disc milling, roller milling, attrition milling, fluid energy milling, ultrasonic milling, high-shear milling, wet milling, dry milling, bead milling, vibratory milling, planetary ball milling, fluid bed milling, pancake milling, loop milling, ball milling, impact milling, colloid milling, air-jet milling, conical milling), delumping, granulating, self-attrition, shredding, pulverization, micronization, ultrasonic treatment, or other methods of size reduction acting through the forces of impact, shear, compression, combinations, or process integrations thereof.

[0256]

[0168] In some embodiments, the size of the metal precursor particles is controlled such that such that the d10 is in the range of from about 10 nm to about 5 mm. In some preferred embodiments, the size of the particles is controlled such that the d10 is in the range of from about 0.1 to about 500 pm. In yet more preferred embodiments, the size of the particles is controlled such that the d10 is in the range of from about 1 to about 250 pm. In some embodiments, the size of the particles is controlled such that the d10 is in the range of from about 0.1 to about 500 pm. In some embodiments, the size of the particles is controlled such that the d10 of the particles are selected to from the following values: about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 pm. In some embodiments, the size of the particles is controlled such that the d90 is in the range of from about 0.1 to about 500 µm. In some embodiments, the d90 of the particles are selected to from the following values: about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm. In some embodiments, the size of the particles is controlled such that the d5 is in the range of from about 0.1 to about 500 µm. In some embodiments, the d5 of the particles are selected to from the following values: about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm. In some embodiments, the size of the particles is controlled such that the d95 is in the range of from about 0.1 to about 500 µm. In some embodiments, the d95 of the particles are selected to from the following values: about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm. In some embodiments, the size of the particles is controlled such that the d1 is in the range of from about 0.1 to about 500 pm. In some embodiments, the d1 the particles are selected to from the following values: about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 pm. In some embodiments, the size of the particles is controlled such that the d99 is in the range of from about 0.1 to about 500 µm. In some embodiments, the d99 the particles are selected to from the following values: about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm.

[0257]

[0169] In some embodiments, the size of the particles of the lithium-selective ion exchange material is increased to yield the final lithium-selective ion exchange material precursor. In some embodiments, the size of the particles of the lithium-selective ion exchange materials is decreased to yield the final lithium-selective ion exchange material precursor. In some embodiments, the size of the particles of the lithium-selective ion exchange materials is first increased, then decreased to yield the final lithium-selective ion exchange material precursor. In some embodiments, the size of the particles of the lithium-selective ion exchange materials is first increased, then decreased and finally classified to yield the final lithium-selective ion exchange material precursor. Said classification occurs by any of the methods, devices, and systems described in “Control of the particle size of the metal precursor, lithium salt precursor, mixed metal oxide, lithium-selective ion exchange material, or lithium-selective ion exchange material.’’

[0258]

[0170] In some embodiments, in the size of the particles of the lithium-selective ion exchange material is increased by extrusion, intrusion, casting, pelletizing, tabletizing, pressing, granulating, calendering, compression molding, thermoforming, sintering, dissolving and recrystallizing, or otherwise treating the particles to form aggregates thereof.

[0259]

[0171] In some embodiments, after the size lithium-selective ion exchange material being increased, the size of the particles of the lithium-selective ion exchange material is reduced prior to use of said lithium-selective ion exchange material to obtain a lithium-selective ion exchange material precursor. In some embodiments, the reduction in the size of the particles is reduced by processing said particles of a metal precursor by a method selected from: crushing, grinding, cutting, attrition, milling (including jet milling, cryo milling, ball milling, hammer milling, pin milling, disc milling, roller milling, attrition milling, fluid energy milling, ultrasonic milling, high-shear milling, wet milling, dry milling, bead milling, vibratory milling, planetary ball milling, fluid bed milling, pancake milling, loop milling, ball milling, impact milling, colloid milling, air-jet milling, conical milling), delumping, granulating, self-attrition, shredding, pulverization, micronization, ultrasonic treatment, or other methods of size reduction acting through the forces of impact, shear, compression, combinations, or process integrations thereof.

[0260]

[0172] In some embodiments, the size of the lithium-selective ion exchange material particles is controlled such that such that the d10 is in the range of from about 10 nm to about 5 mm. InAttorney Docket No.: 733PCT601

[0261] some preferred embodiments, the size of the particles is controlled such that the d10 is in the range of from about 0.1 to about 500 pm. In yet more preferred embodiments, the size of the particles is controlled such that the d10 is in the range of from about 1 to about 250 pm. In some embodiments, the size of the particles is controlled such that the d10 is in the range of from about 0.1 to about 500 pm. In some embodiments, the size of the particles is controlled such that the d10 of the particles are selected to from the following values: about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 pm. In some embodiments, the size of the particles is controlled such that the d90 is in the range of from about 0.1 to about 500 µm. In some embodiments, the d90 of the particles are selected to from the following values: about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm. In some embodiments, the size of the particles is controlled such that the d5 is in the range of from about 0.1 to about 500 µm. In some embodiments, the d5 of the particles are selected to from the following values: about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm. In some embodiments, the size of the particles is controlled such that the d95 is in the range of from about 0.1 to about 500 µm. In some embodiments, the d95 of the particles are selected to from the following values: about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm. In some embodiments, the size of the particles is controlled such that the d1 is in the range of from about 0.1 to about 500 pm. In some embodiments, the d1 the particles are selected to from the following values: about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 pm. In some embodiments, the size of the particles is controlled such that the d99 is in the range of from about 0.1 to about 500 µm. In some embodiments, the d99 the particles are selected to from the following values: about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm.

[0262]

[0173] In some embodiments, the lithium salt precursor is selected from: lithium sulfate, lithium carbonate, lithium nitrate, lithium phosphate, lithium hydroxide, lithium chloride, combinations thereof, hydrates thereof, or size classification cuts thereof.

[0263]

[0174] In some embodiments, the metal precursor is selected from: titanium dioxide, titanium alkoxides, manganese dioxide, manganese oxide, manganese carbonate, manganese acetate, manganese hydroxide, tin oxide, tin acetate, tin sulfate, copper oxide, aluminum oxide, vanadium oxide, silicon dioxide, manganese nitrate, manganese sulfate, manganese phosphate,Attorney Docket No.: 733PCT601

[0264] iron phosphate, ferric nitrate, ferric sulfate, ferrous nitrate, ferrous sulfate, iron oxide, cobalt oxide, NixMnyCo1-x-y(OH)2, NixMnyAl1-x-y(OH)2, solid solutions thereof, or combinations thereof.

[0265]

[0175] In some embodiments, the mixed metal oxide is selected from: LiFePO4, LiMnPO4, Li2TiO3, Li2Ti2O5, Li2MnO3, Li2Mn2O5, Li2SnO3, Li4Ti5O12, Li4Mn5O12, LiTi2O4, LiMn2O4, Li1.6Mn1.6O4, LiAlO2, LiCuO2, LiTiO2, Li4TiO4, Li7Ti11O24, Li3VO4, compounds thereof, nonstoichiometric compounds thereof, modifications thereof, solid solutions thereof, a combination thereof, or size classification cuts thereof.

[0266]

[0176] In some embodiments, the lithium-selective ion exchange material is selected from: LiFePO4, LiMnPO4, Li2TiO3, Li2Ti2O5, Li2MnO3, Li2Mn2O5, Li2SnO3, Li4Ti5O12, Li4Mn5O12, LiTi2O4, LiMn2O4, Li1.6Mn1.6O4, LiAlO2, LiCuO2, LiTiO2, Li4TiO4, Li7Ti11O24, Li3VO4, compounds thereof, nonstoichiometric compounds thereof, modifications thereof, solid solutions thereof, a combination thereof, or size classification cuts thereof. In some embodiments, the lithium-selective on exchange materials is a mixed metal oxide.

[0267]

[0177] Provided herein are material compositions prepared by sizing, controlling the particle size, or otherwise classifying particles of a material. In some embodiments, sizing comprises a size reduction. In some embodiments, sizing comprises reducing average particle size. In some embodiments, sizing comprises controlling the average particle size, so that the size of the particles falls within an acceptable range. In some embodiments, sizing comprises treatment by milling.

[0268]

[0178] In some embodiments, sizing comprises treatment in a crushing mill, a pin mill, a hammer mill, an impact mill, an air classifier mill, a jet mill, or a combination thereof. In some embodiments, sizing comprises treatment in a crashing mill. In some embodiments, the crashing mill comprises a disc mill, a jaw crashing mill, a roller mill, or a combination thereof.

[0269]

[0179] In some embodiments, mixed metal oxides, metal precursor, or lithium-selective ion exchange materials are sieved to control the select particles thereof. In some embodiments, sieving removes particles from the mixed metal oxide that are above a first size threshold, removes particles from the mixed metal oxide that are below a second size threshold, or both. In some embodiments, sieving removes particles from the mixed metal oxide that are above a size threshold. In some embodiments, sieving removes particles from the mixed metal oxide that are below a size threshold. In some embodiments, sieving provides a mixed metal oxide that comprises particles that are below a first size threshold, above a second size threshold, or both. In some embodiments, sieving provides a mixed metal oxide that consists of particles that are below a first size threshold, above a second size threshold, or both. In some embodiments,Attorney Docket No.: 733PCT601

[0270] sieving provides a mixed metal oxide that consists of particles that are above a size threshold. In some embodiments, sieving provides a mixed metal oxide that consists of particles that are below a size threshold. In some embodiments, the size threshold (e.g., the first size threshold, the second size threshold) is selected from: about 10 microns, about 20 microns, about 30 microns, about 40 microns, about 50 microns, about 60 microns, about 70 microns, about 80 microns, about 90 microns, about 100 microns, about 125 microns, about 150 microns, about 175 microns, about 200 microns, about 225 microns, about 250 microns, about 275 microns, about 300 microns, about 325 microns, about 350 microns, about 375 microns, about 400 microns, about 425 microns, about 450 microns, about 475 microns, about 500 microns, about 525 microns, about 550 microns, about 575 microns, about 600 microns, about 650 microns, about 700 microns, about 750 microns, about 800 microns, about 850 microns, about 900 microns, about 950 microns, about 1000 microns, about 1100 microns, about 1200 microns, about 1300 microns, about 1400 microns, and about 1500 microns. In some embodiments, sieving provides a mixed metal oxide with a particle size of ≤ 300 μm. In some embodiments, sieving provides a mixed metal oxide with a particle size of at least 300 μm. In some embodiments, sieving provides a mixed metal oxide with a particle size of at least 500 μm. In some embodiments, sieving provides a mixed metal oxide with a particle size of at least 1000 μm.

[0271]

[0180] In some embodiments, sieving is conducted at a temperature of about 200 K to about 1000 K. In some embodiments, sieving is conducted at a temperature of about 200 K to about 500 K. In some embodiments, sieving is conducted at a temperature of about 500 K to about 750 K. In some embodiments, sieving is conducted at a temperature of about 750 K to about 1000 K. In some embodiments, sieving is conducted at a temperature of about 200 K, about 300 K, about 400 K, about 500 K, about 600 K, about 700 K, about 800 K about 900 K, or about 1000 K.

[0272]

[0181] In some embodiments, the mixed metal oxide provided following sizing or sieving is used for lithium extraction according to any embodiment of a method or system for lithium extraction (e.g., from a liquid resource) as described herein. The utility of the mixed metal oxide provided herein is not limited to use according to the embodiments of methods and systems for lithium extraction described herein, particularly in view of the advantageous properties of such mixed metal oxides that are expounded throughout the present disclosure.

[0273]

[0182] In an aspect, the properties of the metal precursor, lithium salt precursor, matrix material, and / or mixed metal oxide are controlled to yield optimal properties of the lithium-selective ion exchange material. In a related aspect, the properties of the lithium-selective ion exchange material are controlled by (and depend on) the properties of the metal precursor, lithium salt precursor, matrix material, and / or mixed metal oxide they are manufactured from. In a furtherAttorney Docket No.: 733PCT601

[0274] aspect, the properties of the mixed metal oxide are controlled to yield optimal properties of the lithium-selective ion exchange material. For example, the use of mixed metal oxide with high specific surface areas yields a lithium-selective ion exchange material with a high specific surface area, as exemplified in exemplary compositions 5 and derived composition 15. In yet another example, the use of mixed metal oxide with high specific pore volume yields a lithiumselective ion exchange material with a high specific pore volume, as exemplified in exemplary compositions 5 and derived composition 15.

[0275]

[0183] In one aspect, the lithium-selective ion exchange material comprises particles of the mixed metal oxide on their own (i.e. without an optional matrix material). In some embodiments, the mixed metal oxide comprises lithium and a transition metal, wherein said transition metal is selected from titanium or manganese. Thus, the properties of the lithium-ion exchange material correspond to those of the mixed metal oxide. In some embodiments, the mixed metal oxide exhibits a controlled particle size distribution, as in exemplary compositions 4 to 8 in table 1; thus, the lithium-selective ion exchange material composition resulting in using said mixed metal oxide as an ion exchange material exhibit these controlled and advantageous particle size distributions. In these embodiments, said advantageous particle size distribution lead to advantageous properties, including but not limited to the high specific surface area, high pore volume, low pressure drop and fast settling velocity.

[0276]

[0184] In an aspect, the properties of the metal precursor or lithium salt are controlled to yield optimal properties of the mixed metal oxide. In a related aspect, the properties of the mixed metal oxide are controlled by (and depend on) the properties of the metal precursor or lithium salt precursor they are manufactured from. In a further aspect, the properties of the mixed metal oxide, thus controlled by the properties of the metal precursor or lithium salt precursor, are controlled to yield optimal properties of the lithium-selective ion exchange material. For example, the use of metal precursor controlled particle size distribution yields mixed metal oxides with controlled particle size distributions. In a further aspect, mixed metal oxides thus controlled yield lithium-selective ion exchange materials with controlled particle size distributions derived therefrom. For example, exemplary composition 8 (Table 1) has an advantageous particle size distribution that closely reflects the particle size distribution of the manganese dioxide precursor exemplary composition 4 (Table 1). In contrast, exemplary composition 9 has a disadvantageous particle size distribution that closely reflects the particle size distribution of the manganese dioxide precursor exemplary composition 3 (Table 1). Similar conclusions can be drawn from advantageous exemplary composition 5 (derived from exemplary composition 2), compared to disadvantageous exemplary composition 9 (derived fromAttorney Docket No.: 733PCT601

[0277] exemplary composition 1). In these embodiments, said advantageous particle size distribution lead to advantageous properties, including but not limited to the high specific surface area, high pore volume, low pressure drop and fast settling velocity.

[0278]

[0185] It is thus critical to control the properties of metal precursors used in the manufacturing of lithium-selective ion exchange materials to yield optimal mixed metal oxides and lithiumselective ion exchange materials derived therefrom. For example, compositions disclosed herein comprise mixed metal oxides derived from titanium oxide and manganese oxide precursor (exemplary compositions 1 to 4 in Table 1) which exhibit high surface area, porosity, and advantageous particle size distributions. Other precursor without said advantageous properties, including salts or liquid (such as titanium alkoxides, manganese carbonate, manganese acetate, manganese hydroxide, manganese nitrate, manganese sulfate, manganese phosphate, or any other ionic titanium or manganese salts) may result in disadvantageous particle size distributions, low surface area, and low porosity, leading to disadvantageous compositions of mixed metal oxides synthesized therefrom, and lithium-selective ion exchange materials derived therefrom.

[0279] Matrix Materials for coating, embedding, adhering to or otherwise supporting mixed metal oxide particles

[0280]

[0186] In an aspect, the particles of the mixed metal oxide are at least partially coated by, embedded in, adhered to, or otherwise supported by one or more matrix materials.

[0281]

[0187] In an aspect, the size of the particles of the mixed metal oxide used in the preparation, synthesis, of manufacturing of said ion exchange material is controlled, to affect the final size of the particles of the lithium-selective ion exchange material. In an aspect, the size of the particles of the matrix material used in the preparation, synthesis, of manufacturing of said ion exchange material is controlled, to affect the final size of the particles of the lithium-selective ion exchange material. In an aspect, the size of the particles of the matrix material and the mixed metal oxide used in the preparation, synthesis, of manufacturing of said ion exchange material is controlled, to affect the final size of the particles of the lithium-selective ion exchange material.

[0282]

[0188] In an aspect, the mixed metal oxide is embedded in, adhered to, or otherwise supported by a first matrix material, and further embedded in, adhered to, or otherwise supported in a second matrix material to form the final lithium-selective ion exchange material. In some embodiments, the size of the particles of the mixed metal oxide, the first matrix material, the mixed metal oxide embedded in the first matrix material, the second matrix material, or the resulting lithium-selective ion exchange material is controlled. In some embodiments, three orAttorney Docket No.: 733PCT601

[0283] more matrix materials are used to yield the final lithium-selective ion exchange material, and the size of any component forming said material is controlled.

[0284]

[0189] An aspect of the invention disclosed herein is controlling the size of particles of the lithium-selective ion exchange material. In some embodiments, this control is achieved by controlling the size of the mixed metal oxide before said mixed metal oxide is partially coated by, embedded in, adhered to, or otherwise supported by one or more matrix materials. In some embodiments, this control is achieved by controlling the size of the matrix material before said mixed metal oxides is partially coated by, embedded in, adhered to, or otherwise supported by one or more matrix materials. In some embodiments, this control is achieved by controlling the size of both the mixed metal oxide and the matrix material before these are formed into the final lithium-selective ion exchange material.

[0285]

[0190] In an aspect, the size of the particles of the final lithium-selective ion exchange material is controlled. In some embodiments, the size of the particles of lithium salt precursor, metal precursor, the matrix material, any synthesis intermediates, or the final lithium-selective ion exchange material are optionally controlled to yield the final lithium-selective ion exchange material.

[0286]

[0191] In some embodiments, said controlling of the size of the particles of the lithium-selective ion exchange material yield materials with optimal properties for lithium extraction. In some embodiments, said optimal properties include physicochemical, textural, and hydrodynamic properties of the material, including, but not limited to: specific surface area (including as measured by the BET method from N₂ physisorption), porosity, specific pore volume (including as measured by N₂ physisorption), particle size distribution (including dlO and d90 values), pore size distribution (including pore dlO and d90 values), the pressure drop through a packed bed of said material, settling velocity, and lithium extraction properties.

[0287]

[0192] Exemplary embodiment and values of said properties are included in Table 1 and associated examples. This includes exemplary materials 5 to 8, where the size of the mixed metal oxide is controlled prior to it being embedded in, adhered to, or otherwise supported by one or more matrix materials. This further includes material 8 to 23, where the size of the final lithium-selective ion exchange material is further controlled.

[0288]

[0193] In some embodiments, said mixed metal oxide is at least partially coated by, embedded in, adhered to, or otherwise supported by the one or more matrix materials. In some embodiments, said coating, embedding, adhesion, or support is achieved by a method comprising obtaining a first matrix material precursor, and contacting said first matrix material precursor to the mixed metal oxide (including when a lithium-selective ion exchange materialAttorney Docket No.: 733PCT601

[0289] comprises said mixed metal oxide), and optionally treating said matrix-particle mixture to coat, embed, adhered, or otherwise support the particles of the mixed metal oxide in the first matrix material. In some embodiments, the mixed metal oxide is coated by, embedded in, adhered to, or otherwise supported by the first matrix material is the final formulation of lithium-selective ion exchange material. In some embodiments, the mixed metal oxide is coated by, embedded in, adhered to, or otherwise supported by the first matrix is further classified (the size of its particles controlled) to result in an advantageous particle size, textural, and hydrodynamic properties of the final formulation of lithium-selective ion exchange material.

[0290]

[0194] In some embodiments, the mixed metal oxide is coated by, embedded in, adhered to, or otherwise supported by the first matrix, on its own or after further classification (control of its particle size), is further treated to coat, embed, adhered, or otherwise support the particles in a second matrix material. Said coating, embedding, adhesion, or support can be achieved by the methods described for the first matrix material. In some embodiments, multiple treatments result in a final formulation of lithium-selective ion exchange material comprising multiple matrix materials. In some embodiments, the size of particles of any of the intermediates is controlled.

[0291]

[0195] In some embodiments, the first matrix material is a polymer or an oxide. In some embodiments, the first matrix material is a polymer, and the second matrix material is an oxide. In some embodiments, the first matrix material is an oxide, and the second matrix material is a polymer.

[0292]

[0196] In some embodiments, the matrix material is a polymer selected from: polyvinylidene fluoride, polyvinyl fluoride, polyvinyl chloride, polyvinylidene chloride, a chloro-polymer, a fluoro-polymer, a fluoro-chloro-polymer, polyethylene, polypropylene, polyphenylene sulfide, polytetrafluoroethylene, sulfonated polytetrafluoroethylene, polystyrene, polymethyl methacrylate, polydivinylbenzene, polybutadiene, a sulfonated polymer, a carboxylated polymer, polyacrylonitrile, perfluoro-3,6-dioxa-4-methyl-7-octene-sulfonic acid (Nation®), dioxa-4-methyl-7-octene-sulfonic acid, copolymers thereof, or combinations thereof. In some embodiments, the matrix material is polyvinylidene fluoride. In some embodiments, the matrix material is polyvinyl fluoride. In some embodiments, the matrix material is polyvinyl chloride. In some embodiments, the matrix material is poly vinylidene chloride. In some embodiments, the matrix material is polyethylene. In some embodiments, the matrix material is polypropylene. In some embodiments, the matrix material is polyacrylonitrile. In some embodiments, the matrix material is polymethyl methacrylate.

[0293]

[0197] In some embodiments, the matrix material comprises TiO₂, ZrO₂, SiO₂, Al₂O₃, solid solutions thereof, or mixed oxides thereof, or combinations thereof.Attorney Docket No.: 733PCT601

[0294]

[0198] In some embodiments, particles of the matrix material is classified (the size of its particles controlled) before their use to coat, embed, adhered, or otherwise support the particles of the mixed metal oxide. This includes classification of the first, second, or any subsequent matrix material.

[0295]

[0199] In some embodiments, the metal precursor particles rejected by the classification unit are recycled to synthesize a metal precursor. In some embodiments, the mixed metal oxide particles rejected by the classification unit are recycled to synthesize a mixed metal oxide or metal precursor. In some embodiments, the lithium-selective ion exchange material particles rejected by the classification unit are recycled to synthesize a mixed metal oxide or metal precursor. In some embodiments, the matrix material particles rejected by the classification unit are recycled to obtain a matrix material precursor. In some embodiments, said recycling comprising dissolving or digesting said metal precursor, mixed metal oxide, matrix material, or lithiumselective ion exchange material in one or more solvent, and then crystallizing a recycling material therefrom.

[0296]

[0200] In some embodiments, the size of the particles of the matrix material(s) is increased to yield the final matrix material precursor. In some embodiments, the size of the particles of the matrix materials is decreased to yield the final matrix material precursor. In some embodiments, the size of the particles of the matrix materials is first increased, then decreased to yield the final matrix material precursor. In some embodiments, the size of the particles of the matrix materials is first increased, then decreased and finally classified to yield the final matrix material precursor. Said classification occurs by any of the methods, devices, and systems described in “Control of the particle size of the metal precursor, lithium salt precursor, mixed metal oxide, matrix material, or lithium-selective ion exchange material.’’

[0297]

[0201] In some embodiments, in the size of the particles of the matrix material is increased by extrusion, intrusion, casting, pelletizing, tabletizing, pressing, granulating, calendering, compression molding, thermoforming, sintering, dissolving and recrystallizing, or otherwise treating the particles to form aggregates thereof. Exemplary embodiments of such treatment are included in Table 1 and Example 11 to 13.

[0298]

[0202] In some embodiments, after the size matrix material being increased, the size of the particles of the matrix material is reduced prior to use of said matrix material to obtain a matrix material precursor. In some embodiments, the reduction in the size of the particles is reduced by processing said particles of a metal precursor by a method selected from: crushing, grinding, cutting, attrition, milling (including jet milling, cryo milling, ball milling, hammer milling, pin milling, disc milling, roller milling, attrition milling, fluid energy milling, ultrasonic milling,Attorney Docket No.: 733PCT601

[0299] high-shear milling, wet milling, dry milling, bead milling, vibratory milling, planetary ball milling, fluid bed milling, pancake milling, loop milling, ball milling, impact milling, colloid milling, air-jet milling, conical milling), delumping, granulating, self-attrition, shredding, pulverization, micronization, ultrasonic treatment, or other methods of size reduction acting through the forces of impact, shear, compression, combinations, or process integrations thereof.

[0300]

[0203] In some embodiments, the reduction in size of the matrix material precursor is performed at a controlled temperature. In some embodiments, the temperature is controlled to be in the range of: from about 70 K to about 80 K, from about 80 K to about 90 K, from about 90 K to about 100 K, from about 100 K to about 110 K, from about 110 K to about 120 K, from about 120 K to about 130 K, from about 130 K to about 140 K, from about 140 K to about 150 K, from about 150 K to about 160 K, from about 160 K to about 170 K, from about 170 K to about 180 K, from about 180 K to about 190 K, from about 190 K to about 200 K, from about 200 K to about 210 K, from about 210 K to about 220 K, from about 220 K to about 230 K, from about 230 K to about 240 K, from about 240 K to about 250 K, from about 250 K to about 260 K, from about 260 K to about 270 K, from about 270 K to about 280 K, from about 280 K to about 290 K, from about 290 K to about 300 K, from about 300 K to about 310 K, from about 310 K to about 320 K, from about 320 K to about 330 K, from about 330 K to about 340 K, from about 340 K to about 350 K, from about 350 K to about 360 K, from about 360 K to about 370 K, from about 370 K to about 380 K.

[0301]

[0204] In some embodiments, the size of the matrix material particles is controlled such that such that the d₁₀ is in the range of from about 10 nm to about 5 mm. In some preferred embodiments, the size of the particles is controlled such that the d₁₀ is in the range of from about 0.1 to about 500 μm. In yet more preferred embodiments, the size of the particles is controlled such that the d₁₀ is in the range of from about 1 to about 250 μm. In some embodiments, the size of the particles is controlled such that the d10 is in the range of from about 0.1 to about 500 μm. In some embodiments, the size of the particles is controlled such that the d₁₀ of the particles are selected to from the following values: about 0.1 μm, about 0.5 μm, about 1 μm, about 5 μm, about 10 μm, about 25 μm, about 50 μm, about 75 μm, about 100 μm, about 250 μm, about 500 μm. In some embodiments, the size of the particles is controlled such that the d90 is in the range of from about 0.1 to about 500 μm. In some embodiments, the d90 of the particles are selected to from the following values: about 0.1 μm, about 0.5 μm, about 1 μm, about 5 μm, about 10 μm, about 25 μm, about 50 μm, about 75 μm, about 100 μm, about 250 μm, about 500 μm. In some embodiments, the size of the particles is controlled such that the d5 is in the range of from about 0.1 to about 500 μm. In some embodiments, the d5 of the particles are selected to from theAttorney Docket No.: 733PCT601

[0302] following values: about 0.1 μm, about 0.5 μm, about 1 μm, about 5 μm, about 10 μm, about 25 μm, about 50 μm, about 75 μm, about 100 μm, about 250 μm, about 500 μm. In some embodiments, the size of the particles is controlled such that the d95 is in the range of from about 0.1 to about 500 μm. In some embodiments, the d95 of the particles are selected to from the following values: about 0.1 μm, about 0.5 μm, about 1 μm, about 5 μm, about 10 μm, about 25 μm, about 50 μm, about 75 μm, about 100 μm, about 250 μm, about 500 μm. In some embodiments, the size of the particles is controlled such that the d1 is in the range of from about 0.1 to about 500 μm. In some embodiments, the d1 the particles are selected to from the following values: about 0.1 μm, about 0.5 μm, about 1 μm, about 5 μm, about 10 μm, about 25 μm, about 50 μm, about 75 μm, about 100 μm, about 250 μm, about 500 μm. In some embodiments, the size of the particles is controlled such that the d99 is in the range of from about 0.1 to about 500 μm. In some embodiments, the d99 the particles are selected to from the following values: about 0.1 μm, about 0.5 μm, about 1 μm, about 5 μm, about 10 μm, about 25 μm, about 50 μm, about 75 μm, about 100 μm, about 250 μm, about 500 μm.

[0303]

[0205] In some embodiments, the matrix material particles rejected by the classification unit are recycled to obtain a matrix material precursor. In some embodiments, said recycling comprising dissolving or digesting said metal precursor, mixed metal oxide, matrix material, or lithiumselective ion exchange material in one or more solvent, and then crystallizing a recycling material therefrom.

[0304]

[0206] In some embodiments, the matrix material dissolves in said liquid to form a solution. In some embodiments, said matrix material and said liquid form a slurry. In some embodiments, said liquid is water or an aqueous solution. In some embodiments, said liquid is an organic solvent. In some embodiments, said organic solvent is selected from: acetone, ethyl acetate, dichloromethane (DCM), N, N-dimethylformamide (DMF), tetrahydrofuran (THF), N, N-dimethylacetamide (DMAc), chloroform, toluene, methyl ethyl ketone (MEK), anisole, mixtures thereof, solutions thereof, or combinations thereof. In some embodiments, the matrix material is a polymer, and said polymer dissolves in an organic solvent. In some embodiments, said matrix material is a polymer selected from: polyvinylidene fluoride, polyvinyl fluoride, polyvinyl chloride, poly vinylidene chloride, a chloro-polymer, a fluoro-polymer, a fluoro-chloro-polymer, polyethylene, polypropylene, polyphenylene sulfide, polytetrafluoroethylene, sulfonated polytetrafluoroethylene, polystyrene, polymethyl methacrylate, polydivinylbenzene, polybutadiene, a sulfonated polymer, a carboxylated polymer, polyacrylonitrile, perfluoro-3,6-dioxa-4-methyl-7-octene-sulfonic acid (Nafion®), copolymers thereof, or combinations thereof.dioxa-4-methyl-7-octene-sulfonic acid, copolymers thereof, or combinations thereof.Attorney Docket No.: 733PCT601

[0305]

[0207] In some embodiments, the matrix material dissolves in said liquid to form a solution. In some embodiments, said matrix material and said liquid form a slurry. In some embodiments, said liquid is water or an aqueous solution. In some embodiments, said matrix material comprises TiO₂, ZrO₂, SiO₂, Al₂O₃, solid solutions thereof, or mixed oxides thereof, or combinations thereof.

[0306]

[0208] In some embodiments, the matrix material is obtained by processing a matrix material precursor to obtain a matrix material precursor with a controlled particle size, by any of the methods or systems disclosed herein.

[0307]

[0209] Exemplary embodiments of lithium-selective ion exchange material comprising a mixed metal oxide and a matrix material are included in Table 1. Composition 11, 12, and 13 comprise compositions synthesized by the sintering of a mixed metal oxide and a matrix material, including embodiments where the particle size distribution of the mixed metal oxide, matrix materials, and lithium-selective ion exchange material are controlled.

[0308]

[0210] Exemplary embodiments of lithium-selective ion exchange material comprising a mixed metal oxide and a matrix material are included in Table 1. Composition 14 to 17 comprise compositions synthesized by dissolving a polymer in a solvent, and forming a slurry of the dissolved polymer with the mixed metal oxide, including embodiments where the particle size distribution of the mixed metal oxide, matrix materials, and lithium-selective ion exchange material are controlled. Composition 18 and 19 comprise embodiments comprising compositions where a lithium-selective ion exchange material comprising a matrix material and a mixed metal oxide are blended, and their size optimally controlled. Compositions 20 to 21 comprise compositions of lithium-selective ion exchange material comprising a mixed metal oxide and an oxide matrix material. Compositions 22 to 23 comprise compositions of lithium-selective ion exchange material comprising a mixed metal oxide and at least one matrix material.

[0309]

[0211] In these exemplary compositions, methods and systems used for manufacturing of an ion exchange material are disclosed.

[0310]

[0212] In an aspect, the mixed metal oxide are at least partially coated by, embedded in, adhered to, or otherwise supported by the one or more matrix materials. In some embodiments, said coating, embedding, adhesion, or support is achieved by a method comprising obtaining a first matrix material precursor, and contacting said first matrix material precursor to the mixed metal oxide (including when said oxide is a lithium-selective ion exchange material), and optionally treating said matrix-particle mixture to coat, embed, adhered, or otherwise support the particles of the mixed metal oxide in the first matrix material. In some embodiments, the process is additionally repeated with a second matrix material precursor. In some embodiments, theAttorney Docket No.: 733PCT601

[0311] process is additionally repeated with a third matrix material precursor. In some embodiments, the process is additionally repeated with a fourth matrix material precursor. In some embodiments, the process is additionally repeated with a fifth or additional matrix material precursors.

[0312]

[0213] In a further aspect, said first or additional matrix-particle mixture is obtained by mixing said matrix material precursor and particles of the mixed metal oxide. In some embodiments, said mixing is performed in a unit selected from: a blender, a high-speed disperser, an mixing tank, an agitated mixing tank, a multi-shaft mixer, a high-shear mixer, a low-speed mixer, a planetary mixer, a static mixer, an ultrasonic homogenizer, a rotor-stator mixer, a double planetary mixer, a kneader, an extruder, a ribbon blender, a high-pressure homogenizer, a granulator, or a combined process thereof.

[0313]

[0214] In some embodiments, said matrix-particle mixture is further processed to at least partially coat, embed, adhered, or otherwise support the mixed metal oxide within the matrix material, through a process that forms an intermediate composite structure. In some embodiments, said intermediate composite structure is formed by one or more of the processes selected from: extrusion, in-line mixing, casting, pelletizing, tabletizing, mixing, blending, compounding, milling, granulation, calendering, injection molding, compression molding, blow molding, thermoforming, rotational molding, coating, laminating, sintering, pressing, drying, devolatilization, filtration, centrifugation, or combinations thereof.

[0314]

[0215] In some embodiments, said intermediate composite structure is formed by two sequential processes:

[0315] a) First: extruding, casting, granulating, or otherwise forming a continuous stmcture of said matrix-particle mixture;

[0316] b) Second: drying said continuous structure to remove all liquid, thereby yielding the intermediate composite stmcture.

[0317]

[0216] In yet other embodiments, said intermediate composite stmcture is formed by two sequential processes:

[0318] c) First: extruding, pressing, pelletizing, or tabletizing said matrix-particle mixture to form pellets, granules, tablets, or briquettes;

[0319] d) Second: sintering said pellets, granules, tables, or briquettes.

[0320]

[0217] In some embodiments, said drying or sintering is performed at a controlled temperature, and wherein said temperature is in the range of: from about 70 K to about 80 K, from about 80 K to about 90 K, from about 90 K to about 100 K, from about 100 K to about 110 K, from about 110 K to about 120 K, from about 120 K to about 130 K, from about 130 K to about 140 K, fromAttorney Docket No.: 733PCT601

[0321] about 140 K to about 150 K, from about 150 K to about 160 K, from about 160 K to about 170 K, from about 170 K to about 180 K, from about 180 K to about 190 K, from about 190 K to about 200 K, from about 200 K to about 210 K, from about 210 K to about 220 K, from about 220 K to about 230 K, from about 230 K to about 240 K, from about 240 K to about 250 K, from about 250 K to about 260 K, from about 260 K to about 270 K, from about 270 K to about 280 K, from about 280 K to about 290 K, from about 290 K to about 300 K, from about 300 K to about 310 K, from about 310 K to about 320 K, from about 320 K to about 330 K, from about 330 K to about 340 K, from about 340 K to about 350 K, from about 350 K to about 360 K, from about 360 K to about 370 K, from about 370 K to about 380 K.

[0322]

[0218] In some embodiments, said intermediate composite structure is formed by two processes selected from: extruding, pressing, pelletizing, sintering, or tabletizing said matrix-particle mixture to form a continuous structure. In some embodiments, said intermediate composite structure is in the form of pellets, beads, tablets, briquettes, granules, powder, fibers, sheets, films, sheets, strands, flakes, rods, nuggets, discs, cubes, granules, agglomerates, or extrudates. In some embodiments, the intermediate composite structure is further processed to reduce the size of the particles and yield a comminuted composite structure. In some embodiments, the comminuted composite structure is the lithium-selective ion exchange material.

[0323]

[0219] In some embodiments, the size of the particles yielding the comminuted composite structure is reduced by a method selected from: crushing, grinding, cutting, attrition, milling (including jet milling, cryo milling, ball milling, hammer milling, pin milling, disc milling, roller milling, attrition milling, fluid energy milling, ultrasonic milling, high-shear milling, wet milling, dry milling, bead milling, vibratory milling, planetary ball milling, fluid bed milling, pancake milling, loop milling, ball milling, impact milling, colloid milling, air-jet milling, conical milling), delumping, granulating, self-attrition, shredding, pulverization, micronization, ultrasonic treatment, or other methods of size reduction acting through the forces of impact, shear, compression, combinations, or process integrations thereof.

[0324]

[0220] In some embodiments, the size of the particles is controlled such that the dio of the particles is selected to from the following values: about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 pm, about 1 mm. In some embodiments, the size of particles is controlled such that the (I of the particles is selected to from the following values: about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 pm, about 1 mm. In some embodiments, the size of the particles is controlled such that the ds>o of the particles is selected to from the following values: about 0.5Attorney Docket No.: 733PCT601

[0325] μm, about 1 μm, about 5 μm, about 10 μm, about 25 μm, about 50 μm, about 75 μm, about 100 μm, about 250 μm, about 500 μm, about 1 mm. In some embodiments, the size of the particles is controlled such that the d97of the particles is selected to from the following values: about 0.5 μm, about 1 μm, about 5 μm, about 10 μm, about 25 μm, about 50 μm, about 75 μm, about 100 μm, about 250 μm, about 500 μm, about 1 mm.

[0326]

[0221] In some embodiments, the size of the particles is controlled by processing the comminuted composite structure through a size classification. In some embodiments, the comminuted composite structure thus classified is the lithium-selective ion exchange material. In some embodiments, the said size classification unit processes the comminuted composite structure through one or more of the following: dry screening, air classification, wet classification, decantation, sieving, screening, sifting, gravity separation, elutriation, centrifugation, settling, clarification, filtering, or combined processes thereof.

[0327]

[0222] In some embodiments, said dry screening comprises one or more sieves, screens, mechanical vibration devices, or other devices designed to retain particles above a minimum size while allowing smaller particles to pass through. In some embodiments, said air classification comprises one or more devices selected from: gravitational air classifiers, air-jet sieving devices, gravitational inertial air classifiers, centrifugal air classifiers, gyrotor air classifiers, cyclones, or combinations thereof.

[0328]

[0223] In some embodiments, said wet classification comprises one or more devices selected from: a clarifier, a lamellar clarifier, hydrocyclone, a cyclone, an elutriation device, a reflux classifier, a wet sieve, a wet screening device, a vibratory wet screening device, a decantation device, or combinations thereof. In some embodiments, set wet classification devices comprises: A repulping unit, configured to suspend the particles; A wet classification device comprising,

[0329]

[0224] one or more screens configured to retain larger particles while allowing smaller particles to pass and be discarded: components designed to efficiently separate smaller particles, including but not limited to: one ore more spraying devices designed to wash the particles, one or more mechanical vibration devices designed to allow efficient washing of the particles, one or more flow distribution devices configured to efficiently direct the particles into the one or more screens, or a combination thereof; An optional water recycling unit, configured to recycle at least a portion of the water used for the wet classification process.

[0330]

[0225] In some embodiments, the wet classified material is further dried. In some embodiments, said drying is performed in a convection drier, a vacuum drier, or other device designed to remove a liquid from a solid at ambient or elevated temperature.Attorney Docket No.: 733PCT601

[0331]

[0226] In some embodiments, the one or more matrix material(s) are selected from: TiO2, ZrO2, SiO2, Al2O3, solid solutions thereof, or mixed oxides thereof, or combinations thereof.

[0332]

[0227] In some embodiments, the one or more matrix material(s) are selected

[0333] from:poly vinylidene fluoride, polyvinyl fluoride, polyvinyl chloride, poly vinylidene chloride, a chloro-polymer, a fluoro-polymer, a fluoro-chloro-polymer, polyethylene, polypropylene, polyphenylene sulfide, polytetrafluoroethylene, sulfonated polytetrafluoroethylene, polystyrene, polydivinylbenzene, polybutadiene, a sulfonated polymer, a carboxylated polymer, polyacrylonitrile, perfluoro-3,6-dioxa-4-methyl-7-octene-sulfonic acid (Nafion®), copolymers thereof, or combinations thereof. dioxa-4-methyl-7-octene-sulfonic acid, copolymers thereof, or combinations thereof.

[0334]

[0228] In some embodiments, the mass ratio of matrix material to mixed metal oxide to the plurality of particles from about 50:1 to about 1:50. In some embodiments, the mass ratio of matrix material to mixed metal oxide to the plurality of particles from about 1: 1 to about 1:20. In some embodiments, the mass ratio of matrix material to mixed metal oxide to the plurality of particles from about 1:1 to about 1:5.

[0335]

[0229] In some embodiments, the weight percentage (wt%) of the matrix material in the final lithium-selective ion exchange material ranges from about 1 wt% to about 99 wt%. In some embodiments, the weight percentage (wt%) of the matrix material in the final lithium-selective ion exchange material ranges are as follows: about 1 wt% to about 3 wt%, about 3 wt% to about 5 wt%, about 5 wt% to about 7 wt%, about 7 wt% to about 10 wt%, about 10 wt% to about 15 wt%, about 15 wt% to about 20 wt%, about 20 wt% to about 30 wt%, about 30 wt% to about 40 wt%, about 40 wt% to about 50 wt%, about 50 wt% to about 60 wt%, about 60 wt% to about 70 wt%, about 70 wt% to about 80 wt%, about 80 wt% to about 90 wt%, and about 90 wt% to about 99 wt%.

[0336]

[0230] In some embodiments, a first matrix material is selected from: TiO2, ZrO2, SiO2, Al2O3, solid solutions thereof, or mixed oxides thereof, or combinations thereof. In some embodiments, a second matrix material is selected from: polyvinylidene fluoride, polyvinyl fluoride, polyvinyl chloride, polyvinylidene chloride, a chloro-polymer, a fluoro-polymer, a fluoro-chloro-polymer, polyethylene, polypropylene, polyphenylene sulfide, polytetrafluoroethylene, sulfonated polytetrafluoroethylene, polystyrene, polydivinylbenzene, polybutadiene, a sulfonated polymer, a carboxylated polymer, polyacrylonitrile, perfluoro-3,6-dioxa-4-methyl-7-octene-sulfonic acid (Nafion®), copolymers thereof, or combinations thereof.dioxa-4-methyl-7-octene-sulfonic acid, copolymers thereof, or combinations thereof.Attorney Docket No.: 733PCT601

[0337]

[0231] In some embodiments, a first matrix material is selected from: polyvinylidene fluoride, polyvinyl fluoride, polyvinyl chloride, polyvinylidene chloride, a chloro-polymer, a fluoropolymer, a fluoro-chloro-polymer, polyethylene, polypropylene, polyphenylene sulfide, polytetrafluoroethylene, sulfonated polytetrafluoroethylene, polystyrene, polydivinylbenzene, polybutadiene, a sulfonated polymer, a carboxylated polymer, polyacrylonitrile, perfluoro-3,6-dioxa-4-methyl-7-octene-sulfonic acid (Nafion®), copolymers thereof, or combinations thereof.dioxa-4-methyl-7-octene-sulfonic acid, copolymers thereof, or combinations thereof. In some embodiments, a second matrix material is selected from: TiO2, ZrO2, SiO2, Al2O3, solid solutions thereof, or mixed oxides thereof, or combinations thereof.

[0338]

[0232] In some embodiments, at least two, at least three, at least four, or at least five matrix materials are used to coat, embed, adhere, or otherwise supported the mixed metal oxides to form the lithium-selective ion exchange material composition.

[0339] Embodiments comprising advantageous compositions with removal of fine material

[0233] An aspect of the invention disclosed herein are compositions of lithium-selective ion exchange materials with controlled particle sizes. In some embodiments, the particle size of the metal precursor, lithium salt precursor, mixed metal oxide, one or more matrix material(s), lithium-selective ion exchange material, or any mixture thereof is controlled.

[0340]

[0234] In certain advantageous embodiments of the invention disclosed herein, the control of particle sizes is achieved by sizing the material to remove fine particles (fines). In some embodiments, the removal of fines to control particle size and enhance the performance of the lithium-selective ion exchange material. In some embodiments, the removal of fines is advantageous to achieving optimal material properties and ensuring efficient lithium extraction processes. In some embodiments, the removal of fines is advantageous to achieving a lower pressure drop when the material is packed into a fixed bed. In some embodiments, the removal of fines results in lower loss of material to process fluids, including an acidic eluent or liquid resource, during lithium extraction. In some embodiments, the removal of fines results in lower loss of material to process fluids, including an acidic eluent or liquid resource, during lithium extraction because fines that would otherwise be slowly bled into the liquid during the extraction process are removed upfront, before the usage of material for lithium extraction.

[0341]

[0235] It should be understood that compositions comprising the removal of fine material or particles, and systems and methods used to achieve said compositions, can be achieved by any of the systems and methods described in “Control of the particle size of the metal precursor,Attorney Docket No.: 733PCT601

[0342] lithium salt precursor, mixed metal oxide, or lithium-selective ion exchange material.” Herein, other embodiments related to the removal of fine material are described.

[0343]

[0236] In some embodiments, fines are removed from the metal precursor. In some embodiments, fines are removed from the lithium salt precursor. In some embodiments, fines are removed from the mixed metal oxide. In some embodiments, fines are removed from the matrix material(s). In some embodiments, fines are removed from the lithium-selective ion exchange material. In some embodiments, fines are removed from the metal precursor and from the lithium-selective ion exchange material.

[0344]

[0237] In some embodiments, the removal of fines involves the use of specific particle cutoffs. In some embodiments, particle cutoffs are defined by the size thresholds for the particles that are to be removed during the classification (particle size control) process. In some embodiments, these cutoffs can include, but are not limited to, values such as about 0.1 micron, about 1 micron, about 5 microns, 10 microns, about 20 microns, about 30 microns, about 40 microns, about 50 microns, about 60 microns, about 70 microns, about 80 microns, about 90 microns, and about 100 microns.

[0345]

[0238] In some embodiments, the removal of fines can be achieved through various methods, including but not limited to: dry screening, air classification, wet classification, decantation, sieving, screening, sizing, sifting, gravity separation, elutriation, centrifugation, settling, clarification, filtering, magnetic separation, electrostatic separation, flotation, gravity separation, centrifugal separation, and hydrometallurgical separation processes, or combined processes thereof. In some embodiments, this method can be used to remove particles that are either above or below a certain size threshold. In some embodiments, at least one method is used. In some embodiments, each of the methods used have different particle size cutoffs. In some embodiments, each of the methods removes a particular portion of fine material.

[0346]

[0239] In some embodiments, a washing process is employed to enhance the removal of fines. In some embodiments, said washing aids in the removal of fines from the surface of the metal precursor, mixed metal oxide, matrix material, or lithium-selective ion exchange. This washing process can involve various methods, including but not limited to, immersion in a washing solution, spraying, vibration, agitation, ultrasonication, and filtration. In some embodiments, the washing solution can be water, an aqueous solution, or an organic solvent, depending on the nature of the fines and the material being washed. In some embodiments, the material is submerged in the solution and allowed to soak, facilitating the detachment of fines from the surface. Agitation, either mechanical or manual, can be used to enhance the removal process by creating turbulence and increasing the contact between the solution and the fines.Attorney Docket No.: 733PCT601

[0347]

[0240] In some embodiments, surfactants or detergents are added to the washing solution to enhance the removal of fines. Surfactants reduce the surface tension of the solution, increasing its wetting ability and facilitating the detachment of fines from the material's surface. The choice of surfactant depends on the material and the nature of the fines, with common options including non-ionic, anionic, and cationic surfactants.

[0348]

[0241] The efficiency of the washing process is determined by several factors, including the nature and amount of fines, the washing method used, and the conditions of the process (e.g., temperature, agitation speed, and washing time). In some embodiments, the washing efficiency is quantified by measuring the reduction in fines content on the material's surface before and after washing. Techniques such as microscopy, particle size analysis, and surface area measurements can be employed to assess the effectiveness of the washing process.

[0349]

[0242] In some embodiments, the removal of fines through washing results in improved physicochemical properties of the material, such as increased specific surface area, enhanced porosity, and reduced pressure drop during application. These improvements contribute to the overall performance and efficiency of the lithium-selective ion exchange material in various processes, including lithium extraction and other industrial applications.

[0350]

[0243] In some embodiments, the removal of fines from the particle size distribution provides several advantages, including but not limited to improved pressure drop (AP). In some embodiments, the removal of fines reduces the pressure drop across a packed bed of the material, leading to improved flow characteristics and lower energy consumption during lithium extraction processes.

[0351]

[0244] In some embodiments, removing fines can improve the physicochemical, textural, and hydrodynamic properties of the material, such as specific surface area, porosity, and pore volume. In some embodiments, achieving a more uniform particle size distribution enhances the consistency and reliability of the material's performance in various applications. In some embodiments, the removal of fines decreases the settling velocity of the particles, which can be beneficial in processes where stable suspensions are required. In some embodiments, by implementing these methods and focusing on the removal of fines, the resulting lithium-selective ion exchange material exhibits optimal properties for lithium extraction and other applications, ensuring high performance and efficiency.

[0352] Embodiments comprising classified fine material

[0353]

[0245] In an aspect, the particles of a mixed metal oxide are mixed with a composite structure, a comminuted composite structure, a lithium-selective ion exchange material or any classifiedAttorney Docket No.: 733PCT601

[0354] particles thereof. The composition of any of these embodiments may be a lithium-selective ion exchange material. Thus, in this manner, properties of the mixed metal oxides can be combined with other compositions described herein, including compositions comprising a mixed metal oxide a matrix material. This approach may yield lithium-selective ion exchange materials with advantageous properties, or may alternatively serve to better utilize the mixed metal oxide used in its manufacture, or both.

[0355]

[0246] Exemplary embodiments of lithium-selective ion exchange material comprising a mixed metal oxide and a matrix material are included in Table 1. Composition 18 and 19, and 13 comprise such mixtures of a mixed metal oxide with another lithium-selective ion exchange material, yielding a second lithium-selective ion exchange material with advantageous properties.

[0356]

[0247] In some embodiments, said the particles of the mixed metal oxide thus mixed are undersized particles that were rejected during the controlling of the size of the mixed metal oxide described in “Control of the particle size of the metal precursor, lithium salt precursor, mixed metal oxide, or lithium-selective ion exchange material In some embodiments, said the particles of the mixed metal oxide thus mixed are undersized particles that were rejected during the controlling of the size of the mixed metal oxide described in “Embodiments comprising advantageous compositions with removal of fine material.” In some embodiments, the undersized material is further classified prior to mixing it.

[0357]

[0248] In some embodiments, the ratio of mixed metal oxide to lithium-selective ion exchange material is from about 50: 1 to about 1:50 on a mass basis. In some embodiments, the ratio of mixed metal oxide to lithium-selective ion exchange material is selected from approximately: 40:1, 30:1, 20:1, 10:1, 5:1, 2:1, 1:2, 1:5, 1:10, 1:20, 1:30, and 1:40.

[0358]

[0249] In some embodiments, the size of the particles of the final lithium-selective ion exchange material is controlled. In some embodiments, the size of the particles of the mixed metal oxide are controlled to yield the final lithium-selective ion exchange material.

[0359]

[0250] In some embodiments, the size of the particles is controlled to yield particles with specific particle size distributions, as characterized by the dl, d5, dlO, d90, d95, and d99 of the particles. For example, controlling the particle size from dlO to d90 would yield a range where 80% of the particles are within that range. It should be understood that the size of the particles described below can apply to the lithium-selective ion exchange material, or to any components thereof whose size was controlled in the synthesis of said materials, including but not limited to the lithium salt precursor, the metal precursor, the mixed metal oxide, the synthesis mixture, the matrix material, any intermediate materials thereof, or any combinations hereof.Attorney Docket No.: 733PCT601

[0360]

[0251] In some embodiments, the size of the particles is controlled such that the d10is in the range of from about 10 nm to about 5 mm. In some preferred embodiments, the size of the particles is controlled such that the d10is in the range of from about 0.1 to about 500 μm. In yet more preferred embodiments, the size of the particles is controlled such that the d10is in the range of from about 1 to about 250 μm.

[0361]

[0252] In some embodiments, the size of the particles is controlled such that the d10is in the range of from about 0.1 to about 500 μm. In some embodiments, the size of the particles is controlled such that the d10of the particles are selected to from the following values: about 0.1 μm, about 0.5 μm, about 1 μm, about 5 μm, about 10 μm, about 25 μm, about 50 μm, about 75 μm, about 100 μm, about 250 μm, about 500 μm.

[0362]

[0253] In some embodiments, the size of the particles is controlled such that the d90 is in the range of from about 0.1 to about 500 pm. In some embodiments, the d90 of the particles is selected to from the following values: about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 pm.

[0363]

[0254] In some embodiments, the size of the particles is controlled such that the d5 is in the range of from about 0.1 to about 500 pm. In some embodiments, the d5 of the particles is selected to from the following values: about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 pm.

[0364]

[0255] In some embodiments, the size of the particles is controlled such that the d95 is in the range of from about 0.1 to about 500 pm. In some embodiments, the d95 of the particles is selected to from the following values: about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 um.

[0365]

[0256] In some embodiments, the size of the particles is controlled such that the dl is in the range of from about 0.1 to about 500 pm. In some embodiments, the dl of the particles is selected to from the following values: about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 um.

[0366]

[0257] In some embodiments, the size of the particles is controlled such that the d99 is in the range of from about 0.1 to about 500 pm. In some embodiments, the d99 of the particles is selected to from the following values: about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm,Attorney Docket No.: 733PCT601

[0367] about 10 μm, about 25 μm, about 50 μm, about 75 μm, about 100 μm, about 250 μm, about 500 μm.

[0368]

[0258] In an aspect, the size of the particles is controlled by processing the particles through a size classification unit. In some embodiments, the size classification units are designed to retain particles above a cutoff minimum size while allowing smaller particles to pass through. In some embodiments, the cutoff size for the sieving process can be selected from a range of values, including from about 0.1 um to about 0.5 pm, from about 1 um to about 5 pm, from about 10 um to about 25 pm, from about 50 um to about 75 pm, from about 100 um to about 250 pm, and from about 500 pm. The choice of cutoff size depends on the desired particle size distribution and the specific application of the lithium-selective ion exchange material. In some embodiments, the smaller particles that are not retained by the classification device comprise about 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 75%, 90% or 99% of particles of the material before classification.

[0369]

[0259] In some embodiments, said size classification unit comprises on or more: dry screening, air classification, wet classification, decantation, sieving, screening, sifting, gravity separation, elutriation, centrifugation, settling, clarification, filtering, magnetic separation, electrostatic separation, flotation, and hydrometallurgical separation processes, or combined processes thereof.

[0370] Properties of mixed metal oxides and lithium-selective ion exchange materials derived therefrom

[0371]

[0260] In one aspect, provided herein are mixed metal oxides. In some embodiments, a lithiumselective ion exchange materials comprises said mixed metal oxides. In one aspect, provided herein are compositions of mixed metal oxides. In some embodiments, a lithium-selective ion exchange materials comprises one or more compositions of said mixed metal oxides. In some embodiments, said mixed metal oxides at least partially coated by, embedded in, adhered to, or otherwise supported by one or more matrix materials to provide a lithium-selective ion exchange materials. In some embodiments, said lithium-selective ion exchange materials are ion exchange materials. Further provided herein are compositions mixed metal oxides or lithium-selective ion exchange materials derived therefrom.

[0372]

[0261] In a further aspect, the size of the particles comprising said mixed metal oxide, or said lithium-selective ion exchange material derived therefrom, is controlled to achieve certain advantageous properties. In some embodiments, said advantageous properties result in optimal performance for lithium extraction.Attorney Docket No.: 733PCT601

[0373]

[0262] Described herein are some of the properties afforded by these mixed metal oxides or lithium-selective ion exchange materials derived therefrom. It shall be understood that properties described herein can apply to the mixed metal oxide or the lithium-selective ion exchange material.

[0374]

[0263] In some embodiments, the disclosed materials possess controlled textural properties that enhance their performance in specific applications. For example, materials with high surface area and optimal pore size distribution are particularly effective in exchanging lithium and protons. In a further example, certain textural properties and particle sizes result in advantageous pressure drop through a packed bed of said material, leading to efficient flow of process fluids used for lithium extraction in lithium extraction devise, as described in sections “Process of extracting lithium from a liquid resource” and “Devices and vessels for beds of an ion exchange material”.

[0375]

[0264] In some embodiments, such mixed metal oxides or lithium-selective ion exchange materials derived therefrom have advantageous mechanical stability. In some embodiments, measurements of mechanical stability include bulk crush strength and attrition resistance. In some embodiments, the mixed metal oxide or lithium-selective ion exchange materials derived therefrom has a bulk crush strength greater than 10 N / cm2. In some embodiments, the mixed metal oxide has a bulk crush strength greater than about 10 N / cm2. In some embodiments, the mixed metal oxide or lithium-selective ion exchange materials derived therefrom has a bulk crush strength greater than 10 N / cm2, 9 N / cm2, 8 N / cm2, 7 N / cm2, 6 N / cm2, or 5 N / cm2. In some embodiments, the mixed metal oxide or lithium-selective ion exchange materials derived therefrom has a bulk crush strength of at least 5 N / cm2, at least 7.5 N / cm2, or at least 10 N / cm2. In some embodiments, the bulk crush strength is measured using ASTM D7084. In some embodiments, the mixed metal oxide has an attrition resistance at most 7%. In some embodiments, the mixed metal oxide or lithium-selective ion exchange materials derived therefrom has an attrition resistance at most about 7%. In some embodiments, the mixed metal oxide or lithium-selective ion exchange materials derived therefrom has an attrition resistance at most about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, or about 15%. In some embodiments, the mixed metal oxide or lithium-selective ion exchange materials derived therefrom has an attrition resistance < 12%, < 10%, or < 7%. In some embodiments, the attrition resistance of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom is measured using ASTM D4058.

[0376]

[0265] In some embodiments, the advantageous mechanical stability of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom increases the service lifetime of theAttorney Docket No.: 733PCT601

[0377] mixed metal oxide or lithium-selective ion exchange materials derived therefrom, as compared to the lifetime of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom as a component of another construct or in isolation when used in methods for lithium extraction. Service lifetime can be quantified in terms of the number of ion exchange cycles conducted before the mixed metal oxide or lithium-selective ion exchange materials derived therefrom is replaced or permanently taken out of service. Service lifetime can be quantified in terms of the cumulative amount of lithium produced by the mixed metal oxide or lithiumselective ion exchange materials derived therefrom before it is replaced or permanently taken out of service. In some embodiments, the advantageous mechanical stability of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom preserves the advantageous porosity of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom. In some embodiments, the advantageous mechanical stability of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom decreases the cost for producing a given quantity of lithium using direct lithium extraction from a liquid resource.

[0378]

[0266] In one aspect, provided herein are mixed metal oxide or lithium-selective ion exchange materials derived therefroms or lithium-selective ion exchange materials derived therefrom. In some embodiments, such mixed metal oxide or lithium-selective ion exchange materials derived therefroms have advantageous porosity. In some embodiments, such advantageous porosity reduces the pressure drop across a packed bed of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom. In some embodiments, porosity is measured as surface area, total pore volume, average pore volume, pore size distribution, or a combination thereof.

[0379]

[0267] In some embodiments, the mixed metal oxide or lithium-selective ion exchange materials derived therefrom or lithium-selective ion exchange materials derived therefrom has a surface area of about 10 m2 / g to about 100 m2 / g. In some embodiments, the mixed metal oxide or lithium-selective ion exchange materials derived therefrom has a surface area of about 10 m2 / g to about 20 m2 / g, about 10 m2 / g to about 25 m2 / g, about 10 m2 / g to about 30 m2 / g, about 10 m2 / g to about 35 m2 / g, about 10 m2 / g to about 40 m2 / g, about 10 m2 / g to about 45 m2 / g, about 10 m2 / g to about 50 m2 / g, about 10 m2 / g to about 60 m2 / g, about 10 m2 / g to about 70 m2 / g, about 10 m2 / g to about 80 m2 / g, about 10 m2 / g to about 100 m2 / g, about 20 m2 / g to about 25 m2 / g, about 20 m2 / g to about 30 m2 / g, about 20 m2 / g to about 35 m2 / g, about 20 m2 / g to about 40 m2 / g, about 20 m2 / g to about 45 m2 / g, about 20 m2 / g to about 50 m2 / g, about 20 m2 / g to about 60 m2 / g, about 20 m2 / g to about 70 m2 / g, about 20 m2 / g to about 80 m2 / g, about 20 m2 / g to about 100 m2 / g, about 25 m2 / g to about 30 m2 / g, about 25 m2 / g to about 35 m2 / g, about 25 m2 / g to about 40 m2 / g, about 25 m2 / g to about 45 m2 / g, about 25 m2 / g to about 50 m2 / g, about 25 m2 / g to about 60 m2 / g, aboutAttorney Docket No.: 733PCT601

[0380] 25 m2 / g to about 70 m2 / g, about 25 m2 / g to about 80 m2 / g, about 25 m2 / g to about 100 m2 / g, about 30 m2 / g to about 35 m2 / g, about 30 m2 / g to about 40 m2 / g, about 30 m2 / g to about 45 m2 / g, about 30 m2 / g to about 50 m2 / g, about 30 m2 / g to about 60 m2 / g, about 30 m2 / g to about 70 m2 / g, about 30 m2 / g to about 80 m2 / g, about 30 m2 / g to about 100 m2 / g, about 35 m2 / g to about 40 m2 / g, about 35 m2 / g to about 45 m2 / g, about 35 m2 / g to about 50 m2 / g, about 35 m2 / g to about 60 m2 / g, about 35 m2 / g to about 70 m2 / g, about 35 m2 / g to about 80 m2 / g, about 35 m2 / g to about 100 m2 / g, about 40 m2 / g to about 45 m2 / g, about 40 m2 / g to about 50 m2 / g, about 40 m2 / g to about 60 m2 / g, about 40 m2 / g to about 70 m2 / g, about 40 m2 / g to about 80 m2 / g, about 40 m2 / g to about 100 m2 / g, about 45 m2 / g to about 50 m2 / g, about 45 m2 / g to about 60 m2 / g, about 45 m2 / g to about 70 m2 / g, about 45 m2 / g to about 80 m2 / g, about 45 m2 / g to about 100 m2 / g, about 50 m2 / g to about 60 m2 / g, about 50 m2 / g to about 70 m2 / g, about 50 m2 / g to about 80 m2 / g, about 50 m2 / g to about 100 m2 / g, about 60 m2 / g to about 70 m2 / g, about 60 m2 / g to about 80 m2 / g, about 60 m2 / g to about 100 m2 / g, about 70 m2 / g to about 80 m2 / g, about 70 m2 / g to about 100 m2 / g, or about 80 m2 / g to about 100 m2 / g. In some embodiments, the mixed metal oxide or lithiumselective ion exchange materials derived therefrom has a surface area of about 10 m2 / g, about 20 m2 / g, about 25 m2 / g, about 30 m2 / g, about 35 m2 / g, about 40 m2 / g, about 45 m2 / g, about 50 m2 / g, about 60 m2 / g, about 70 m2 / g, about 80 m2 / g, or about 100 m2 / g. In some embodiments, the mixed metal oxide or lithium-selective ion exchange materials derived therefrom has a surface area of at least about 10 m2 / g, about 20 m2 / g, about 25 m2 / g, about 30 m2 / g, about 35 m2 / g, about 40 m2 / g, about 45 m2 / g, about 50 m2 / g, about 60 m2 / g, about 70 m2 / g, or about 80 m2 / g. In some embodiments, the mixed metal oxide or lithium-selective ion exchange materials derived therefrom has a surface area of at most about 20 m2 / g, about 25 m2 / g, about 30 m2 / g, about 35 m2 / g, about 40 m2 / g, about 45 m2 / g, about 50 m2 / g, about 60 m2 / g, about 70 m2 / g, about 80 m2 / g, or about 100 m2 / g.

[0381]

[0268] In some embodiments, the mixed metal oxide or lithium-selective ion exchange materials derived therefrom has a total pore volume of about 0.001 mL / g to about 0.1 mL / g. In some embodiments, the mixed metal oxide or lithium-selective ion exchange materials derived therefrom has a total pore volume of about 0.001 mL / g to about 0.005 mL / g, about 0.001 mL / g to about 0.008 mL / g, about 0.001 mL / g to about 0.01 mL / g, about 0.001 mL / g to about 0.015 mL / g, about 0.001 mL / g to about 0.018 mL / g, about 0.001 mL / g to about 0.02 mL / g, about 0.001 mL / g to about 0.05 mL / g, about 0.001 mL / g to about 0.06 mL / g, about 0.001 mL / g to about 0.07 mL / g, about 0.001 mL / g to about 0.08 mL / g, about 0.001 mL / g to about 0.1 mL / g, about 0.005 mL / g to about 0.008 mL / g, about 0.005 mL / g to about 0.01 mL / g, about 0.005 mL / g to about 0.015 mL / g, about 0.005 mL / g to about 0.018 mL / g, about 0.005 mL / g to about 0.02Attorney Docket No.: 733PCT601

[0382] mL / g, about 0.005 mL / g to about 0.05 mL / g, about 0.005 mL / g to about 0.06 mL / g, about 0.005 mL / g to about 0.07 mL / g, about 0.005 mL / g to about 0.08 mL / g, about 0.005 mL / g to about 0.1 mL / g, about 0.008 mL / g to about 0.01 mL / g, about 0.008 mL / g to about 0.015 mL / g, about 0.008 mL / g to about 0.018 mL / g, about 0.008 mL / g to about 0.02 mL / g, about 0.008 mL / g to about 0.05 mL / g, about 0.008 mL / g to about 0.06 mL / g, about 0.008 mL / g to about 0.07 mL / g, about 0.008 mL / g to about 0.08 mL / g, about 0.008 mL / g to about 0.1 mL / g, about 0.01 mL / g to about 0.015 mL / g, about 0.01 mL / g to about 0.018 mL / g, about 0.01 mL / g to about 0.02 mL / g, about 0.01 mL / g to about 0.05 mL / g, about 0.01 mL / g to about 0.06 mL / g, about 0.01 mL / g to about 0.07 mL / g, about 0.01 mL / g to about 0.08 mL / g, about 0.01 mL / g to about 0.1 mL / g, about 0.015 mL / g to about 0.018 mL / g, about 0.015 mL / g to about 0.02 mL / g, about 0.015 mL / g to about 0.05 mL / g, about 0.015 mL / g to about 0.06 mL / g, about 0.015 mL / g to about 0.07 mL / g, about 0.015 mL / g to about 0.08 mL / g, about 0.015 mL / g to about 0.1 mL / g, about 0.018 mL / g to about 0.02 mL / g, about 0.018 mL / g to about 0.05 mL / g, about 0.018 mL / g to about 0.06 mL / g, about 0.018 mL / g to about 0.07 mL / g, about 0.018 mL / g to about 0.08 mL / g, about 0.018 mL / g to about 0.1 mL / g, about 0.02 mL / g to about 0.05 mL / g, about 0.02 mL / g to about 0.06 mL / g, about 0.02 mL / g to about 0.07 mL / g, about 0.02 mL / g to about 0.08 mL / g, about 0.02 mL / g to about 0.1 mL / g, about 0.05 mL / g to about 0.06 mL / g, about 0.05 mL / g to about 0.07 mL / g, about 0.05 mL / g to about 0.08 mL / g, about 0.05 mL / g to about 0.1 mL / g, about 0.06 mL / g to about 0.07 mL / g, about 0.06 mL / g to about 0.08 mL / g, about 0.06 mL / g to about 0.1 mL / g, about 0.07 mL / g to about 0.08 mL / g, about 0.07 mL / g to about 0.1 mL / g, or about 0.08 mL / g to about 0.1 mL / g. In some embodiments, the mixed metal oxide or lithium-selective ion exchange materials derived therefrom has a total pore volume of about 0.001 mL / g, about 0.005 mL / g, about 0.008 mL / g, about 0.01 mL / g, about 0.015 mL / g, about 0.018 mL / g, about 0.02 mL / g, about 0.05 mL / g, about 0.06 mL / g, about 0.07 mL / g, about 0.08 mL / g, or about 0.1 mL / g. In some embodiments, the mixed metal oxide or lithium-selective ion exchange materials derived therefrom has a total pore volume of at least about 0.001 mL / g, about 0.005 mL / g, about 0.008 mL / g, about 0.01 mL / g, about 0.015 mL / g, about 0.018 mL / g, about 0.02 mL / g, about 0.05 mL / g, about 0.06 mL / g, about 0.07 mL / g, or about 0.08 mL / g. In some embodiments, the mixed metal oxide or lithium-selective ion exchange materials derived therefrom has a total pore volume of at most about 0.005 mL / g, about 0.008 mL / g, about 0.01 mL / g, about 0.015 mL / g, about 0.018 mL / g, about 0.02 mL / g, about 0.05 mL / g, about 0.06 mL / g, about 0.07 mL / g, about 0.08 mL / g, or about 0.1 mL / g..Attorney Docket No.: 733PCT601

[0383]

[0269] In some embodiments, the mixed metal oxide or lithium-selective ion exchange materials derived therefrom comprises micropores, mesopores, and macropores with diameters ranging between about 5 Ångstroms and 10 microns.

[0384]

[0270] In some embodiments, the mixed metal oxide or lithium-selective ion exchange materials derived therefrom has a pore size distribution with a characteristic D50 value. The parameter D50 specifies that 50% of the pores are larger than the specified value, and 50% of the pores are smaller than the specified value. In some embodiments, the D50 value is about 1 mm. In some embodiments, the D50 value is about 2 mm. In some embodiments, the D50 value is from about 0.4 mm to about 3 mm. In some embodiments, the D50 value is from about 1 mm to about 10 mm. In some embodiments, the D50 value is about 0.4 mm, about 1 mm, about 2 mm, about 3 mm, about 4 mm, about 5 mm, about 6 mm, about 7 mm, about 8 mm, about 9 mm, or about 10 mm. In some embodiments, the D50 value is from about 70 microns to about 700 microns. In some embodiments, the D50 value is from about 10 microns to about 70 microns. In some embodiments, the D50 value is from about 1 microns to about 10 microns. In some embodiments, the D50 value is from about 0.1 microns to about 1 microns.

[0385]

[0271] In some embodiments, liquids (e.g., a liquid resource, brine, an acidic solution) are flowed through a packed bed of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom. In some embodiments, the advantageous porosity of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom reduces the pressure required to flow liquids through the packed bed. In some embodiments, the pressure required to flow liquids through the packed bed is at most 10 psi, at most 9 psi, at most 8 psi, at most 7 psi, at most 6 psi, at most 5 psi, at most 4 psi, at most 3 psi, at most 2 psi, or at most 1 psi. In some embodiments, the flow distance through the packed bed is about 10 cm, about 25 cm, about 50 cm, about 75 cm, about 100 cm, about 200 cm, about 300 cm, about 400 cm, about 500 cm, about 600 cm, about 700 cm, about 800 cm, about 900 cm, about 1 meter, about 1.5 meters, about 2 meters, or at least 2 meters. In some embodiments, the flow distance through the packed bed is at most about 1 meter. In some embodiments, the flow distance through the packed bed is greater than about 1 meter. In some embodiments, the flow distance through the packed bed is coincident (i.e., aligns with) with the longest dimension of the packed bed. In some embodiments, the flow distance through the packed bed is orthogonal (i.e., perpendicular) to the longest dimension of the packed bed. In some embodiments, a mixed metal oxide or lithiumselective ion exchange materials derived therefrom with a larger particle size is selected to further reduce the pressure required to flow liquids through the packed bed.Attorney Docket No.: 733PCT601

[0386]

[0272] In some embodiments of the lithium extraction process, during ion exchange, binders bound to the surface of the mixed metal oxide limit mass transport due to the low surface area and low porosity observed with existing ion exchange bead manufacturing methods. In some embodiments described herein, the high surface areas and high porosities achieved through the use of binders and pore forming processes described herein, allow larger particle sizes and additional particle morphologies, leading to advantageous mass transport of lithium and protons to and from the mixed metal oxide, leading to increased performance in lithium extraction.

[0387]

[0273] In some embodiments, the advantageous porosity of the mixed metal oxide or lithiumselective ion exchange materials derived therefrom increases the rate of lithium uptake from solution by the mixed metal oxide or lithium-selective ion exchange materials derived therefrom within the mixed metal oxide or lithium-selective ion exchange materials derived therefrom. In some embodiments, the advantageous porosity of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom increases the purity of lithium produced by methods of lithium extraction that utilize the mixed metal oxide or lithium-selective ion exchange materials derived therefrom. In some embodiments, the advantageous porosity of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom decreases the cost for producing a given quantity of lithium using direct lithium extraction from a liquid resource. In some embodiments, the advantageous porosity of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom increases the diffusion of lithium to and from the active surface of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom. In some embodiments, the advantageous porosity of the lithium sorbent composite increases the diffusion of protons to and from the active surface of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom. In some embodiments, the advantageous porosity of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom increases the effectiveness factor for utilization of mixed metal oxide or lithium-selective ion exchange materials derived therefrom. In some embodiments, the advantageous porosity of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom increases utilization of mixed metal oxide for lithium absorption and elution.

[0388]

[0274] In some embodiments, the advantageous surface area of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom increases the rate of lithium uptake from solution or liquid resource. In some embodiments, the advantageous surface area of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom increases the purity of lithium produced by methods of lithium extraction that utilize the mixed metal oxide. In some embodiments, the advantageous surface area of the mixed metal oxide or lithium-Attorney Docket No.: 733PCT601

[0389] selective ion exchange materials derived therefrom decreases the cost for producing a given quantity of lithium using direct lithium extraction from a liquid resource. In some embodiments, the advantageous surface area of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom increases the diffusion of lithium to and from the active surface of the mixed metal oxide. In some embodiments, the advantageous surface area of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom increases the diffusion of protons to and from the active surface of the mixed metal oxide. In some embodiments, the advantageous surface area of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom increases the effectiveness factor for utilization of mixed metal oxide. In some embodiments, the advantageous surface area of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom increases utilization of mixed metal oxide for lithium absorption and elution.

[0390]

[0275] In one aspect, provided herein are mixed metal oxides or lithium-selective ion exchange materials derived therefrom. In some embodiments, such mixed metal oxides have advantageous chemical stability. In some embodiments, said advantageous chemical stability preserves the advantageous porosity of the mixed metal oxide. In some embodiments, said advantageous chemical stability leads to a minimal dissolution of the lithium-selective ion exchange material, the binder, or both when the mixed metal oxide is used in a method of lithium extraction. In some embodiments, said advantageous chemical stability leads to a minimal dissolution of the lithium-selective ion exchange material, the binder, or both when the mixed metal oxide is contacted to an acidic solution.

[0391]

[0276] In one aspect, the composition of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom exhibits particles of a certain particle size. In one aspect, the composition of the particles of the mixed metal oxide or lithium-selective ion exchange materials derived therefrom exhibits particles of controlled particle size. In some embodiments, the size of the particles is described by the particle size distribution. Exemplary embodiments of particle size distributions of compositions disclosed herein are included in Example 5 to 8. Embodiments with specific particle size distributions can be characterized by the dl, d5, dlO, d90, d95, and d99 of the particles. For example, controlling the particle size from dlO to d90 would yield a range where 80% of the particles are within that range. It should be understood that the size of the particles described below can apply to the lithium-selective ion exchange material, or to any components thereof whose size was controlled in the synthesis of said materials, including but not limited to the lithium salt precursor, the metal precursor, the mixedAttorney Docket No.: 733PCT601

[0392] metal oxide, the synthesis mixture, the matrix material, any intermediate materials thereof, or any combinations hereof.

[0393]

[0277] In some embodiments, the size of the particles is such that the d10is in the range of from about 10 nm to about 5 mm. In some preferred embodiments, the size of the particles is such that the d10is in the range of from about 0.1 to about 500 µm. In yet more preferred embodiments, the size of the particles is such that the d10is in the range of from about 1 to about 250 µm.

[0394]

[0278] In some embodiments, the size of the particles is such that the d10 is in the range of from about 0.1 to about 500 µm. In some embodiments, the size of the particles is such that the d10of the particles are selected to from the following values: about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm.

[0395]

[0279] In some embodiments, the size of the particles is such that the d90 is in the range of from about 0.1 to about 500 µm. In some embodiments, the d90 of the particles are selected to from the following values: about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm.

[0396]

[0280] In some embodiments, the size of the particles is such that the d5 is in the range of from about 0.1 to about 500 µm. In some embodiments, the d5 of the particles are selected to from the following values: about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm.

[0397]

[0281] In some embodiments, the size of the particles is such that the d95 is in the range of from about 0.1 to about 500 µm. In some embodiments, the d95 of the particles are selected to from the following values: about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm.

[0398]

[0282] In some embodiments, the size of the particles is such that the d1 is in the range of from about 0.1 to about 500 µm. In some embodiments, the d1 the particles are selected to from the following values: about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm.

[0399]

[0283] In some embodiments, the size of the particles is such that the d99 is in the range of from about 0.1 to about 500 µm. In some embodiments, the d99 the particles are selected to from the following values: about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm.

[0400]

[0284] In certain preferred embodies, the particle size is such as to lead to advantageous properties of the lithium-selective ion exchange material. In some embodiments, these advantageous properties are hydrodynamic properties. Particular hydrodynamic properties areAttorney Docket No.: 733PCT601

[0401] often advantageous for incorporation of the lithium-selective ion exchange material into systems for commercial lithium extraction. Such systems and processes often require advantageous hydrodynamic properties of lithium-selective ion exchange materials, which makes said materials suitable for flowing liquids, including liquid resources and acids, over packed beds or fluidized beds of ion exchange materials. Such systems and processes often require specific hydrodynamic properties that make said ion-exchange materials amenable to transport and conveyance through systems for lithium extraction.

[0402]

[0285] In one aspect, the composition of the mixed metal oxide or lithium-selective ion exchange materials are formed into a packed bed through which process fluids, including a liquid resource and an acidic eluent solution, are flown. Packed beds of ion exchange materials, and devices and vessels that contain such packed beds, are described in “Devices and vessels for beds of an ion exchange material” and “An ion exchange material contained within vessels with minimal flow distance.”

[0403]

[0286] In some embodiments, it is advantageous for packed beds of particles of the lithiumselective ion exchange material to exhibit a specific pressure drop. In some embodiments, said pressure drop is relatively low. In some embodiments, said pressure drop is relatively high. In some embodiments, said pressure drop varies depending on the fluid. In some embodiments, the pressure drop is controlled by the compositions of the material, including the mixed metal oxide, matrix material, or a combination thereof. In some embodiments, the shape of the particle results, as controlled by its manufacturing method, controls the pressure drop. In some embodiments, the particle size distribution, as controlled by its manufacturing method, controls the pressure drop.

[0404]

[0287] In some embodiments, the pressure drop of the fluid flowing through a packed bed of said particles is at most 50 psi / cm at a superficial velocity of 5 cm / min. Exemplary compositions including the values of pressure drop they exhibit are included in Table 1.

[0405]

[0288] In some embodiments, the fluid is water. In some embodiments, the fluid is brine. In some embodiments, the fluid is a liquid resource comprising lithium. In some embodiments, the fluid is an aqueous solution. In some embodiments, the fluid a wash solution. In some embodiments, the fluid is an acidic eluent solution. In some embodiments, the fluid is an eluate, lithium eluate, or synthetic lithium solution.

[0406]

[0289] In some embodiments, the flow velocity of the fluid through the bed of the particles of the lithium-selective ion exchange material is from about 0.01 to about 0.05 cm / min, from about 0.05 to about 0.1 cm / min, from about 0.1 to about 0.5 cm / min, from about 0.5 to about 1 cm / min, from about 1 to about 2 cm / min, from about 2 to about 5 cm / min, from about 5 to aboutAttorney Docket No.: 733PCT601

[0407] 10 cm / min, from about 10 to about 20 cm / min, from about 20 to about 50 cm / min, or from about 50 to about 100 cm / min. The specific flow velocity may be selected based on the desired hydrodynamic properties and efficiency of the lithium extraction process.

[0408]

[0290] In certain embodiments, the length of the bed of the ion exchange material ranges from about 1 cm to about 5 cm, from about 5 cm to about 10 cm, from about 10 cm to about 25 cm, from about 25 cm to about 50 cm, from about 50 cm to about 75 cm, from about 75 cm to about 100 cm, from about 100 cm to about 150 cm, from about 150 cm to about 200 cm, from about 200 cm to about 300 cm, from about 300 cm to about 400 cm, or from about 400 cm to about 500 cm (5 meters). The specific length may be selected based on the desired hydrodynamic properties and efficiency of the lithium extraction process.

[0409]

[0291] In some embodiments, the packed bed of the particles of the lithium-selective ion exchange material exhibits a pressure drop measured at a certain superficial velocity. In some embodiments, the superficial velocity at which the pressure drop is measured is from about 0.01 cm / min to about 10 m / min. In some embodiments, the pressure drop is measured at a superficial velocity of about 5 cm / min. In some embodiments, the pressure drop is measured at a superficial velocity of about 2 cm / min. In some embodiments, the pressure drop is measured at a superficial velocity of about 3 cm / min. In some embodiments, the pressure drop is measured at a superficial velocity of about 4 cm / min. In some embodiments, the pressure drop is measured at a superficial velocity of about 6 cm / min. In some embodiments, the pressure drop is measured at a superficial velocity of about 7 cm / min. In some embodiments, the pressure drop is measured at a superficial velocity of about 0.1 cm / min, about 1 cm / min, about 2 cm / min, about 3 cm / min, about 4 cm / min, about 6 cm / min, about 7 cm / min, about 8 cm / min, about 9 cm / min, about 10 cm / min, about 100 cm / min, about 5 m / min, or about 10 m / min.

[0410]

[0292] In some embodiments, the packed bed of the particles of the lithium-selective ion exchange material exhibits a pressure drop of at most about 5 psi / cm as water flows through the bed at a superficial velocity of about 1 cm / min, at most about 5 psi / cm as water flows through the bed at a superficial velocity of about 0.1 cm / min, at most about 5 psi / cm as water flows through the bed at a superficial velocity of about 0.5 cm / min, at most about 5 psi / cm as water flows through the bed at a superficial velocity of about 2 cm / min, at most about 5 psi / cm as water flows through the bed at a superficial velocity of about 5 cm / min, at most about 5 psi / cm as water flows through the bed at a superficial velocity of about 10 cm / min, at most about 5 psi / cm as water flows through the bed at a superficial velocity of about 50 cm / min, or at most about 5 psi / cm as water flows through the bed at a superficial velocity of about 100 cm / min. In some embodiments, the packed bed of the particles of the lithium-selective ion exchangeAttorney Docket No.: 733PCT601

[0411] material exhibits a pressure drop of at most about 1 psi / cm as water flows through the bed at a superficial velocity of about 0.1 cm / min, about 0.5 cm / min, about 1 cm / min, about 2 cm / min, about 3 cm / min, about 4 cm / min, about 5 cm / min, about 10 cm / min, about 50 cm / min, or about 100 cm / min. In some embodiments, the packed bed of the particles of the lithium-selective ion exchange material exhibits a pressure drop of at most about 3 psi / cm as water flows through the bed at a superficial velocity of about 0.1 cm / min, about 0.5 cm / min, about 1 cm / min, about 2 cm / min, about 3 cm / min, about 4 cm / min, about 5 cm / min, about 10 cm / min, about 50 cm / min, or about 100 cm / min. In some embodiments, the packed bed of the particles of the lithiumselective ion exchange material exhibits a pressure drop of at most about 7 psi / cm as water flows through the bed at a superficial velocity of about 0.1 cm / min, about 0.5 cm / min, about 1 cm / min, about 2 cm / min, about 3 cm / min, about 4 cm / min, about 5 cm / min, about 10 cm / min, about 50 cm / min, or about 100 cm / min. In some embodiments, the packed bed of the particles of the lithium-selective ion exchange material exhibits a pressure drop of at most about 10 psi / cm as water flows through the bed at a superficial velocity of about 0.1 cm / min, about 0.5 cm / min, about 1 cm / min, about 2 cm / min, about 3 cm / min, about 4 cm / min, about 5 cm / min, about 10 cm / min, about 50 cm / min, or about 100 cm / min. In some embodiments, the packed bed of the particles of the lithium-selective ion exchange material exhibits a pressure drop of at most about 25 psi / cm as water flows through the bed at a superficial velocity of about 0.1 cm / min, about 0.5 cm / min, about 1 cm / min, about 2 cm / min, about 3 cm / min, about 4 cm / min, about 5 cm / min, about 10 cm / min, about 50 cm / min, or about 100 cm / min. In some embodiments, the packed bed of the particles of the lithium-selective ion exchange material exhibits a pressure drop of at most about 50 psi / cm as water flows through the bed at a superficial velocity of about 0.1 cm / min, about 0.5 cm / min, about 1 cm / min, about 2 cm / min, about 3 cm / min, about 4 cm / min, about 5 cm / min, about 10 cm / min, about 50 cm / min, or about 100 cm / min. In some embodiments, the packed bed of the particles of the lithium-selective ion exchange material exhibits a pressure drop of at most about 100 psi / cm as water flows through the bed at a superficial velocity of about 0.1 cm / min, about 0.5 cm / min, about 1 cm / min, about 2 cm / min, about 3 cm / min, about 4 cm / min, about 5 cm / min, about 10 cm / min, about 50 cm / min, or about 100 cm / min.

[0412]

[0293] In some embodiments, the packed bed of the particles of the lithium-selective ion exchange material exhibits a pressure drop of at most 0.1 psi / cm, at most 1 psi / cm, at most 2 psi / cm, at most 5 psi / cm, at most 1 psi / cm, at most 3 psi / cm, at most 10 psi / cm, at most 20 psi / cm, at most 40 psi / cm, at most 80 psi / cm, or at most 100 psi / cm.

[0413]

[0294] Superficial velocity, as used herein, refers to the flow velocity of a fluid passing through a packed bed of ion exchange materials, measured in units of distance per time (e.g., cm / min). ItAttorney Docket No.: 733PCT601

[0414] is defined as the volumetric flow rate of the fluid divided by the cross-sectional area of the bed perpendicular to the flow direction, without accounting for the presence of the particles within the bed. Stated differently, this can be referred as the empty bed superficial velocity.

[0415]

[0295] In some embodiments, the pressure drop would be higher if the particle size of the particles of the metal precursor, mixed metal oxide, or comminuted composite structure from which the lithium-selective ion exchange material were not controlled to yield the compositions disclosed herein.

[0416]

[0296] In some embodiments, the compositions disclosed herein exhibit a certain settling velocity. In some embodiments, the settling velocity is controlled by the compositions of the material, including the mixed metal oxide, matrix material, or a combination thereof. In some embodiments, the shape of the particle results, as controlled by its manufacturing method, controls the settling velocity. In some embodiments, the particle size distribution, as controlled by its manufacturing method, controls the settling velocity. Exemplary compositions with embodied settling velocities are included in Table 1.

[0417]

[0297] In some embodiments, the composition of the lithium-selective ion exchange material is characterized by the settling velocity of the particles in water at room temperature, wherein the settling velocity is generally from about 1 mm / min to about 10 m / min. In some embodiments, the composition of the lithium-selective ion exchange material is characterized by the settling velocity of the particles in water at room temperature, wherein the settling velocity is at least about 0.1 cm / min, at least about 0.5 cm / min, at least about 1 cm / min, at least about 2 cm / min, at least about 5 cm / min, at least about 10 cm / min, at least about 20 cm / min, at least about 50 cm / min, at least about 100 cm / min, at least about 500 cm / min, or at least about 1,000 cm / min. In some embodiments, the composition of the lithium-selective ion exchange material is characterized by the settling velocity of the particles in water at room temperature, wherein the settling velocity is at most about 0.1 cm / min, at least about 0.5 cm / min, at least about 1 cm / min, at least about 2 cm / min, at least about 5 cm / min, at least about 10 cm / min, at least about 20 cm / min, at least about 50 cm / min, at least about 100 cm / min, at least about 500 cm / min, or at least about 1,000 cm / min. In some embodiments, the composition of the lithium-selective ion exchange material is characterized by the settling velocity of the particles in water at room temperature, wherein the settling velocity is at most about 0.1 cm / min, from about 0.5 to about 1 cm / min, from about 1 to about 2 cm / min, from about 2 to about 5 cm / min, from about 5 to about 10 cm / min, from about 10 to about 20 cm / min, from about 20 to about 50 cm / min, from about 50 to about 100 cm / min, from about 100 to about 500 cm / min, or from about 500 to about 1,000 cm / min.Attorney Docket No.: 733PCT601

[0418]

[0298] n some embodiments, the composition of the lithium-selective ion exchange material is characterized by the settling velocity of the particles in water, wherein the settling velocity is generally from about 1 mm / min to about 10 m / min. In some embodiments, the composition of the lithium-selective ion exchange material is characterized by the settling velocity of the particles in water, wherein the settling velocity is from about 0.1 to about 0.5 cm / min, from about 0.5 to about 1 cm / min, from about 1 to about 2 cm / min, from about 2 to about 5 cm / min, from about 5 to about 10 cm / min, from about 10 to about 20 cm / min, from about 20 to about 50 cm / min, from about 50 to about 100 cm / min, from about 100 to about 500 cm / min, or from about 500 to about 1,000 cm / min. In some embodiments, the composition of the lithiumselective ion exchange material is characterized by the settling velocity of the particles in water, wherein the settling velocity is at most about 0.1 cm / min, from about 0.5 to about 1 cm / min, from about 1 to about 2 cm / min, from about 2 to about 5 cm / min, from about 5 to about 10 cm / min, from about 10 to about 20 cm / min, from about 20 to about 50 cm / min, from about 50 to about 100 cm / min, from about 100 to about 500 cm / min, or from about 500 to about 1,000 cm / min. In some embodiments, these settling velocities are observed in a temperature ranging from about 250 K to about 450 K. In some embodiments, these settling velocities are observed in a temperature ranging from about 250 to about 260 K, from about 260 to about 270 K, from about 270 to about 280 K, from about 280 to about 290 K, from about 290 to about 300 K, from about 300 to about 310 K, from about 310 to about 320 K, from about 320 to about 330 K, from about 330 to about 340 K, from about 340 to about 350 K, from about 350 to about 360 K, from about 360 to about 370 K, from about 370 to about 380 K, from about 380 to about 390 K, from about 390 to about 400 K, from about 400 to about 410 K, from about 410 to about 420 K, from about 420 to about 430 K, from about 430 to about 440 K, or from about 440 to about 450 K.

[0419]

[0299] In some embodiments, these compositions are designed to enhance the performance of lithium-selective ion exchange materials in various applications, including but not limited to water treatment and lithium extraction. In some preferred embodiments, the specified settling velocities ensure optimal performance and efficiency in practical applications.

[0420]

[0300] In some embodiments, the morphology of the particles of the lithium-selective ion exchange material is characterized by their size, shape, and surface properties, which are critical to their performance in lithium extraction processes. The particles may exhibit various shapes, including but not limited to spherical, ellipsoidal, cylindrical, or irregular geometries, which can be controlled during the manufacturing process to optimize the pressure drop and settling velocity.Attorney Docket No.: 733PCT601

[0421]

[0301] In some embodiments, the surface of the particles may be smooth or rough, and the roughness can be tailored to enhance the surface area available for ion exchange. In some embodiments, the particles have a porous structure, with a porosity that is controlled to balance the mechanical strength and the accessibility of the lithium-selective sites. In some embodiments, the pore size distribution, which can range from micro- to mesopores, is designed to maximize the interaction with lithium ions while minimizing the resistance to fluid flow.

[0422]

[0302]

[0423] Impact of the particle size of the metal precursor, lithium salt precursor, mixed metal oxide, matrix material, or lithium-selective ion exchange material on its properties

[0303] In some embodiments, the particle size of the metal precursor, lithium salt precursor, mixed metal oxide, matrix material, or lithium-selective ion exchange material significantly impacts its properties, including the ion exchange properties of the lithium-selective ion exchange mateial. For example, in some embodiments, a smaller particle size can lead to a higher surface area, which enhances the material's ion exchange capacity and efficiency in lithium extraction processes.

[0424]

[0304] In some embodiments, the particle size distribution is controlled during the manufacturing process to optimize the settling velocity and pressure drop across the packed bed of the ion exchange material. For example, in some embodiments, particles with a more uniform size distribution exhibit better flow characteristics and reduce the energy required for pumping fluids through the bed. In some embodiments, the controlled morphology, including the size and shape of the particles, influences their mechanical strength and the accessibility of lithiumselective ion exchange. In some embodiments, optimizing the particle size and distribution can balance the mechanical strength and the hydrodynamic properties, thereby improving the overall performance and efficiency of the lithium extraction process.

[0425]

[0305] In this manner, by selecting advantageous particle sizes, the properties of the lithiumselective ion exchange material is optimized for lithium extraction.

[0426] Lithium-selective ion exchange materials

[0427]

[0306] In one aspect, the present disclosure provides lithium-selective ion exchange materials. In another aspect, the present disclosure provides methods for preparing said lithium-selective ion exchange materials. In a further aspect, the present disclosure provides methods for using said lithium-selective ion exchange materials in methods for lithium extraction, such as lithium extraction from a liquid resource. The foregoing description, provides a variety of non-limitingAttorney Docket No.: 733PCT601

[0428] embodiments, features, and considerations for providing a lithium-selective ion exchange materials from a mixed metal oxide.

[0429]

[0307] In some embodiments, the lithium-selective ion exchange materials comprise a mixed metal oxide produced by the methods and systems described herein. In some embodiments, the lithium-selective ion exchange materials comprise a lithium-selective ion exchange material. In some embodiments, the lithium-selective ion exchange material is an ion exchange material. In some embodiments, the lithium-selective ion exchange materials of the disclosure serve as an ion exchange material in a method, device, or system for lithium extraction. Accordingly, the lithium-selective ion exchange materials of the present disclosure can be used in conjunction with at least the methods for lithium extraction, the devices for lithium extraction, and the systems for lithium extraction described throughout the present disclosure. Upon consideration of the disclosure as a whole, it will be appreciated that the lithium-selective ion exchange materials provided herein can be used in a variety of adaptations of and alternatives to the methods for lithium extraction, the devices for lithium extraction, and the systems for lithium extraction described throughout the present disclosure.

[0430]

[0308] In one aspect, provided herein are lithium-selective ion exchange materials. Further provided herein are methods of preparing such lithium-selective ion exchange materials, wherein said methods can comprise obtaining a sorbent-binder mixture and mixing the sorbent-binder mixture to form a sorbent-binder semisolid or a sorbent-binder slurry.

[0431]

[0309] For the purposes of this disclosure, the binder may be equivalently referred to as a “structural matrix material” or “matrix material”. As such, additional embodiments of the lithium-selective ion exchange material are contemplated in the section “Beads Comprising a Lithium-selective ion exchange material and a Structural Matrix Material.”

[0432]

[0310] In some embodiments, the sorbent-binder mixture comprises a lithium-selective ion exchange material. The lithium-selective ion exchange material can be any lithium-selective ion exchange material described in any section of the present disclosure. For the purposes of the present disclosure, a lithium-selective ion exchange material is an active material according to some embodiments. In some embodiments, the lithium-selective ion exchange material is an ion exchange material. In some embodiments, the lithium-selective ion exchange material is a lithium-selective ion exchange material.

[0433]

[0311] In some embodiments, the lithium-selective ion exchange material is a lithium titanium oxide. In some embodiments, the lithium-selective ion exchange material is provided by contacting a lithium titanium oxide to an acidic solution, thereby exchanging, partially or wholly, lithium ions from the lithium titanium oxide with hydrogen ions from the acidicAttorney Docket No.: 733PCT601

[0434] solution. In some embodiments, the lithium-selective ion exchange material is a lithium manganese oxide. In some embodiments, the lithium-selective ion exchange material is provided by contacting a lithium manganese oxide to an acidic solution, thereby exchanging, partially or wholly, lithium ions from the lithium manganese oxide with hydrogen ions from the acidic solution. In some embodiments, the lithium-selective ion exchange material comprises Li4Mn5O12, Li4Ti5O12, Li2TiO3, Li2MnO3, Li2SnO3, LiMn2O4, Li1.6Mn1.6O4, LiAlO2, LiCuO2, LiTiO2, Li4TiO4, Li7Ti11O24, Li3VO4, Li2Si2O7, LiFePO4, LiMnPO4, Li2CuP2O7, Al(OH)3, a solid solution thereof, or a combination thereof.

[0435]

[0312] The lithium-selective ion exchange material can be further characterized by its average particle size or particle size distribution. In some embodiments, the lithium-selective ion exchange material used in preparing the lithium-selective ion exchange materials has a characteristic average particle size or particle size distribution. As such, the lithium-selective ion exchange material used to prepare the sorbent-binder mixture can be in the form of particles, such as ion exchange particles. In some embodiments, the D50 of the lithium-selective ion exchange material is within the inclusive range of about 1 to about 100 microns. In some embodiments, the D50 of the lithium-selective ion exchange material is about 1 microns. In some embodiments, the D50 of the lithium-selective ion exchange material is about 5 microns. In some embodiments, the D50 of the lithium-selective ion exchange material is about 10 microns. In some embodiments, the D50 of the lithium-selective ion exchange material is about 15 microns. In some embodiments, the D50 of the lithium-selective ion exchange material is about 20 microns. In some embodiments, the D50 of the lithium-selective ion exchange material is about 30 microns. In some embodiments, the D50 of the lithium-selective ion exchange material is about 40 microns. In some embodiments, the D50 of the lithium-selective ion exchange material is about 60 microns. In some embodiments, the D50 of the lithium-selective ion exchange material is about 70 microns. In some embodiments, the D50 of the lithiumselective ion exchange material is about 80 microns. In some embodiments, the D50 of the lithium-selective ion exchange material is about 90 microns. In some embodiments, the D50 of the lithium-selective ion exchange material is about 100 microns. The parameter D50 specifies that 50% of the particles are larger than the specified value, and 50% of the particles are smaller than the specified value.

[0436]

[0313] In some embodiments, the sorbent-binder mixture comprises a binder. In some embodiments, the sorbent-binder mixture comprises a binder and a lithium-selective ion exchange material. In some embodiments, the sorbent-binder mixture comprises multiple binders. In some embodiments, the sorbent-binder mixture comprises two binders. In someAttorney Docket No.: 733PCT601

[0437] embodiments, the sorbent-binder mixture comprises three binders. In some embodiments, the sorbent-binder mixture comprises four, five, or at least five binders. In some embodiments, the sorbent-binder mixture comprises a lithium-selective ion exchange material and at least one binder. When the sorbent-binder mixture comprises at least one binder, each of said binders can be selected independently. It shall be understood that, unless specified otherwise, the embodiments of a binder described herein are each contemplated for use both with additional binders and without additional binders.

[0438]

[0314] In some embodiments, the sorbent-binder mixture is further characterized by the mass ratio of the lithium-selective ion exchange material to the binder (e.g., one or more binders) in the sorbent-binder mixture. In some embodiments, the mass ratio of the lithium-selective ion exchange material to the binder is about 1:10,000 to about 10,000:1. In some embodiments, the mass ratio of the lithium-selective ion exchange material to the binder is about 1:1,000 to about 1,000:1. In some embodiments, the mass ratio of the lithium-selective ion exchange material to the binder is about 1:100 to about 100:1. In some embodiments, the mass ratio of the lithiumselective ion exchange material to the binder is about 1: 100 to about 10:1. In some embodiments, the mass ratio of the lithium-selective ion exchange material to the binder is about 1:100 to about 1:1. In some embodiments, the mass ratio of the lithium-selective ion exchange material to the binder is about 1:100, about 1:90, about 1:80, about 1:70, about 1:60, about 1:50, about 1:45, about 1:40, about 1:35, about 1:30, about 1:25, about 1:20, about 1:15, about 1:10, about 1:9, about 1:8, about 1:7, about 1:6, about 1:5, about 1:4, about 1:3, about 1:2, about 1:1.8, about 1:1.6, about 1:1.4, about 1:1.2, about 1:1.1, or about 1:1.

[0439]

[0315] In some embodiments, the sorbent-binder mixture comprises one or more binders. When the sorbent-binder mixture comprises at least one binder, the sorbent-binder mixture can be further characterized by the mass ratios of one binder to another binder. In some embodiments, the sorbent-binder mixture comprises two binders (e.g., a first binder and a second binder). In some embodiments, the mass ratio of the first binder to the second binder is about 1:100 to about 1:1. In some embodiments, the sorbent-binder mixture comprises three binders (e.g., a first binder, a second binder, and a third binder). In some embodiments, the mass ratio of the first binder to the second binder can be about 1: 100 to about 1:1, and the mass ratio of the first binder to the third binder can be about 1: 100 to about 1:1. In some embodiments, the mass ratio of the first binder to the second binder can be about 1: 100 to about 1:1, and the mass ratio of the second binder to the third binder can be about 1: 100 to about 1: 1. In some embodiments, the sorbent-binder mixture comprises at least three binders.Attorney Docket No.: 733PCT601

[0440]

[0316] In some embodiments, the binder comprises silica or a silica precursor. In some embodiments, the binder comprises silica. In some embodiments, the silica is porous, amorphous, or both. In some embodiments, the binder comprises a silica precursor. In some embodiments, a silica precursor is a chemical compound or material comprising silicon that can be modified to provide silica. For example, a silica precursor can be modified by heating to provide silica. For example, a silica precursor can be modified by chemical decomposition to provide silica. For example, a silica precursor can be modified by contacting the silica precursor to one or more chemical reagents to provide silica. For example, a silica precursor can be modified by hydrolysis, condensation, or a combination thereof to provide silica. In some embodiments, the silica precursor comprises colloidal silica, a tetraalkyl orthosilicate, fumed silica, a silicate and / or its dissolved water glasses, a natural source of silica, or a combination thereof.

[0441]

[0317] In some embodiments, the silica precursor comprises colloidal silica. In some embodiments, the colloidal silica comprises siloxide groups (Si-O-groups) and counterions. In some embodiments, the colloidal silica comprises counterions selected from sodium, ammonium, hydrogen, and a combination thereof. The colloidal silica can be further characterized by its average particle size or particle size distribution. In some embodiments, the colloidal silica used in preparing the lithium-selective ion exchange materials has a characteristic average particle size or particle size distribution. In some embodiments, the average particle size of the colloidal silica is within the inclusive range of about 5 to about 100 nm. In some embodiments, the average particle size of the colloidal silica is within the inclusive range of about 5 to about 25 nm. In some embodiments, the average particle size of the colloidal silica is within the inclusive range of about 5 to about 50 nm. In some embodiments, the average particle size of the colloidal silica is within the inclusive range of about 25 to about 100 nm. In some embodiments, the average particle size of the colloidal silica is within the inclusive range of about 50 to about 100 nm. The colloidal silica can be further characterized by its surface area. In some embodiments, the colloidal silica used in preparing the lithium-selective ion exchange materials has a characteristic surface area. In some embodiments, the colloidal silica has a surface area within the inclusive range of about 100 to about 350 m2 / g. In some embodiments, the colloidal silica has a surface area within the inclusive range of about 100 to about 200 m2 / g. In some embodiments, the colloidal silica has a surface area within the inclusive range of about 200 to about 350 m2 / g. In some embodiments, the colloidal silica has a surface area within the inclusive range of about 300 to about 350 m2 / g.Attorney Docket No.: 733PCT601

[0442]

[0318] In some embodiments, the binder comprises alumina or an alumina precursor. In some embodiments, the binder comprises alumina. In some embodiments, the alumina is porous, amorphous, or both. In some embodiments, the binder comprises an alumina precursor. In some embodiments, an alumina precursor is a chemical compound or material comprising aluminum that can be modified to provide alumina. For example, an alumina precursor can be modified by heating to provide alumina. For example, an alumina precursor can be modified by chemical decomposition to provide alumina. For example, an alumina precursor can be modified by contacting the alumina precursor to one or more chemical reagents to provide alumina. For example, an alumina precursor can be modified by hydrolysis, condensation, or a combination thereof to provide alumina. In some embodiments, the alumina precursor comprises boehmite, pseudoboehmite, gibbsite, bayerite, aluminum chloride, aluminum hydroxide, or a combination thereof.

[0443]

[0319] In some embodiments, the alumina precursor comprises boehmite. In some embodiments, boehmite is an aluminum oxide hydroxide mineral with the chemical formula AlO2H. In some embodiments, boehmite is a component of bauxite ores. In some embodiments, boehmite is crystalline. In some embodiments, boehmite crystallizes in the orthorhombic space group Amam. Following calcination, the boehmite can be further characterized by its surface area. In some embodiments, upon calcination the boehmite has a surface area within the inclusive range of about 100 to about 450 m2 / g. In some embodiments, upon calcination the boehmite has a surface area within the inclusive range of about 100 to about 200 m2 / g. In some embodiments, upon calcination the boehmite has a surface area within the inclusive range of about 200 to about 300 m2 / g. In some embodiments, upon calcination the boehmite has a surface area within the inclusive range of about 300 to about 450 m2 / g.

[0444]

[0320] In some embodiments, the alumina precursor comprises pseudoboehmite. In some embodiments, pseudoboehmite is an aluminum oxide hydroxide mineral with the chemical formula AlO2H. In some embodiments, pseudoboehmite is comprises finely crystalline boehmite. In some embodiments, the water content of pseudoboehmite is higher than the water content of boehmite. Following calcination, the pseudoboehmite can be further characterized by its surface area. In some embodiments, upon calcination the pseudoboehmite has a surface area within the inclusive range of about 100 to about 450 m2 / g. In some embodiments, upon calcination the pseudoboehmite has a surface area within the inclusive range of about 100 to about 200 m2 / g. In some embodiments, upon calcination the pseudoboehmite has a surface area within the inclusive range of about 200 to about 300 m2 / g. In some embodiments, uponAttorney Docket No.: 733PCT601

[0445] calcination the pseudoboehmite has a surface area within the inclusive range of about 300 to about 450 m2 / g.

[0446]

[0321] In some embodiments, the alumina precursor comprises gibbsite. In some embodiments, gibbsite is an aluminum hydroxide mineral with the chemical formula Al(OH)3. In some embodiments, the gibbsite is bayerite. In some embodiments, bayerite is gibbsite with a monoclinic crystal structure. In some embodiments, gibbsite has a crystal structure that is monoclinic, triclinic, or a combination thereof. Following calcination, the bayerite can be further characterized by its surface area. In some embodiments, upon calcination the bayerite has a surface area within the inclusive range of about 100 to about 450 m2 / g. In some embodiments, upon calcination the bayerite has a surface area within the inclusive range of about 100 to about 200 m2 / g. In some embodiments, upon calcination the bayerite has a surface area within the inclusive range of about 200 to about 300 m2 / g. In some embodiments, upon calcination the bayerite has a surface area within the inclusive range of about 300 to about 450 m2 / g.

[0447]

[0322] In some embodiments, the alumina precursor comprises aluminum chloride. In some embodiments, the alumina precursor comprises aluminum hydroxide.

[0448]

[0323] In some embodiments, the binder comprises a metal oxide or a metal oxide precursor. In some embodiments, the metal oxide is yttria (Y2O3), zirconia (ZrO2), titania (TiO2), or a combination thereof. In some embodiments, the metal oxide precursor is an yttria, a zirconia precursor, a titania precursor, or a combination thereof.

[0449]

[0324] In some embodiments, the binder comprises a mixed metal oxide or a mixed metal oxide precursor. In some embodiments, the mixed metal oxide is a silicon aluminum oxide. In some embodiments, the mixed metal oxide precursor is a silicon aluminum oxide precursor. In some embodiments, the silicon aluminum oxide precursor comprises silica, alumina, a silica precursor, an alumina precursor, or a combination thereof. In some embodiments, the mixed metal oxide is porous, amorphous, or both. In some embodiments, the silicon aluminum oxide precursor comprises amorphous silica alumina, bentonite, callanite, a natural zeolite, a synthetic zeolite, or a combination thereof.

[0450] Beads Comprising a Lithium-selective ion exchange material and a Structural Matrix Material

[0451]

[0325] In some embodiments, lithium-selective ion exchange materials are formed into a bead, said bead comprising an ion exchange material. Therefore, embodiments described herein for “ion exchange beads’’ should be understood to apply to any embodiments for “ion exchange material”, or for any material composition comprising an ion exchange material, including butAttorney Docket No.: 733PCT601

[0452] not limited to coated ion exchange material(s), beads comprising coated ion exchange material(s), ion exchange materials embedded in a structural support, ion exchange materials embedded in a matrix, composites comprising ion exchange material(s), lithium-selective ion exchange materials - wherein the lithium-selective ion exchange material comprises an ion exchange material, or combinations thereof.

[0453]

[0326] In some embodiments, the ion exchange beads are formed by mixing of ion exchange material, a structural matrix material, and a filler material. In some embodiments, the ion exchange beads are formed by mixing of ion exchange material and a structural matrix material. In some embodiments, said matrix material is referred to as a structural support. In some embodiments, the ion exchange beads are formed by mixing of ion exchange material and a structural matrix material. In some embodiments, the components of an ion exchange bead combined to form a physical mixture or a composite. In some embodiments wherein an ion exchange bead comprises a filler material, the filler material can be removed therefrom to form network of pores therein and yield a porous ion exchange bead. The filler material is dispersed in the bead in such a way to leave behind a pore structure that enables transport of lithium and hydrogen with fast kinetics. In some embodiments, an ion exchange bead comprises one or more ion exchange materials, one or more structural matrix materials, and one or more filler materials.

[0454]

[0327] In some embodiments, the mixed metal oxide is embedded in, adhered to, or otherwise supported by a structural to form the porous structure.

[0455]

[0328] In some embodiments, the structural matrix material is selected from the following list: a polymer, an oxide, a phosphate, or combinations thereof. In some embodiments, a structural matrix material is selected from the following list: polyvinyl fluoride, polyvinylidene difluoride, polyvinyl chloride, polyvinylidene dichloride, polyethylene, polypropylene, polyphenylene sulfide, polytetrafluoroethylene, polytetrafluoroethylene, sulfonated polytetrafluoroethylene, polystyrene, polydivinylbenzene, polybutadiene, sulfonated polymer, carboxylated polymer, Nafion, copolymers thereof, and combinations thereof. In some embodiments, a structural matrix material is selected from the following list: polyvinylidene difluoride, polyvinyl chloride, sulfonated polytetrafluoroethylene, polystyrene, polydivinylbenzene, copolymers thereof, or combinations thereof. In some embodiments, a structural matrix material is selected from the following list: titanium dioxide, zirconium dioxide, silicon dioxide, solid solutions thereof, or combinations thereof. In some embodiments, the structural matrix material is selected for its thermal durability, acid resistance, and / or other chemical resistance.

[0456]

[0329] In some embodiments, the porous ion exchange bead is formed by a process comprising mixing ion exchange particles, structural matrix material, and filler material together at once. InAttorney Docket No.: 733PCT601

[0457] some embodiments, the porous ion exchange bead is formed by a process comprising mixing the ion exchange particles and the structural matrix material, and then mixing the resulting mixture with the filler material. In some embodiments, the porous ion exchange bead is formed by a process comprising mixing the ion exchange particles and the filler material, and then mixing the resulting mixture with the structural matrix material. In some embodiments, the porous ion exchange bead is formed by a process comprising mixing the structural matrix material and the filler material, and then mixing the resulting mixture with the ion exchange particles.

[0458]

[0330] In some embodiments, the porous ion exchange bead is formed by a process comprising mixing the ion exchange particles, the structural matrix material, and / or the filler material with a solvent that dissolves one or more of the components of the mixture. In some embodiments, the porous ion exchange bead is formed by a process comprising mixing the ion exchange particles, the structural matrix material, and / or the filler material as dry powders in a mixer or ball mill. In some embodiments, the porous ion exchange bead is formed by a process comprising mixing the ion exchange particles, the structural matrix material, and / or the filler material in a spray drier.

[0459]

[0331] In some embodiments, the structural matrix material is a polymer that is dissolved in a solvent and subsequently mixed with the ion exchange particles and / or filler material using a solvent from the following list: N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, dimethylacetamide, methyl ethyl ketone, or combinations thereof. In some embodiments, the filler material is a salt that is dissolved in a solvent and subsequently mixed with the ion exchange particles and / or structural matrix material using a solvent from the following list: water, ethanol, isopropyl alcohol, acetone, or combinations thereof.

[0460]

[0332] In some embodiments, the ion exchange beads comprise a filler material that is a salt that can be dissolved out of the ion exchange bead to form a network of pores within the ion exchange bead. In some embodiments, the ion exchange beads comprise a filler material that is a salt that can be dissolved out of the ion exchange bead using a solution selected from the following list: water, ethanol, isopropyl alcohol, a surfactant mixture, an acid, a base, or combinations thereof. In some embodiments, the ion exchange beads comprise a filler material that is a material that thermally decomposes to form a gas at high temperature such that the thermal decomposition of the filler material forms a network of pores within the ion exchange bead. In some embodiments, the ion exchange beads comprise a filler material that is a material that thermally decomposes to form a gas at high temperature wherein the gas is selected from the following list: water vapor, oxygen, nitrogen, chlorine, carbon dioxide, nitrogen oxides, organic vapors, or combinations thereof.Attorney Docket No.: 733PCT601

[0461]

[0333] In some embodiments, the mixed ion exchange beads have a pore size distribution with a characteristic D50 value. The parameter D50 specifies that 50% of the pores are larger than the specified value, and 50% of the pores are smaller than the specified value. In some embodiments, the D50 value is about 1 mm. In some embodiments, the D50 value is about 2 mm. In some embodiments, the D50 value is from about 0.4 mm to about 3 mm. In some embodiments, the D50 value is from about 1 mm to about 10 mm. In some embodiments, the D50 value is about 0.4 mm, about 1 mm, about 2 mm, about 3 mm, about 4 mm, about 5 mm, about 6 mm, about 7 mm, about 8 mm, about 9 mm, or about 10 mm. In some embodiments, the D50 value is from about 70 microns to about 700 microns. In some embodiments, the D50 value is from about 10 microns to about 70 microns. In some embodiments, the D50 value is from about 1 microns to about 10 microns. In some embodiments, the D50 value is from about 0.1 microns to about 1 microns.

[0462]

[0334] In some embodiments, a coating material used to form a coating on the lithium-selective ion exchange material. In some embodiments, a coating material used to form a coating on an ion exchange material or on ion exchange particles that comprise an ion exchange material is selected from the following list: a carbide, a nitride, an oxide, a phosphate, a fluoride, a polymer, carbon, a carbonaceous material, or combinations thereof. In some embodiments, the coating material comprises an oxide different from the oxide of the ion exchange material. In some embodiments, a coating material is selected from the following list: TiCh, ZrCh, MoO2, SnCh, Nb2C>5, Ta20, SiCh, Li2TiO3, Li2ZrO3, Li2> S 1O3, L^MnCh, LizMoCh, LiNbO3, LiTaOi, AIPO4, LaPO4, ZrP2O7, MOP2O7, MO2P3O12, BaSO4, AIF3, SiC. TiC, ZrC, Si3N4, ZrN, BN, carbon, graphitic carbon, amorphous carbon, hard carbon, diamond-like carbon, solid solutions thereof, or combinations thereof. In some embodiments, a coating material is selected from the following list: TiO2, ZrO2, MoO2, SiO2, Li2TiO3, Li2ZrO3, Li2SiO3, Li2MnO3, LiNbO3, AlF3, SiC, Si3N4, graphitic carbon, amorphous carbon, diamond-like carbon, or combinations thereof.

[0463]

[0335] In some embodiments, the ion exchange material or the ion exchange particles comprising an ion exchange material have a coating comprising a coating material with a thickness selected from the following list: at most 1 nm, at most 10 nm, at most 100 nm, or at most 1,000 nm. In some embodiments, the coating material has a thickness selected from the following list: at most 1 nm, at most 10 nm, or at most 100 nm.

[0464]

[0336] In some embodiments, the ion exchange material and the coating material form one or more concentration gradients such that the chemical composition of coated ion exchange particles comprising the ion exchange material and the coating material ranges between two or more compositions. In some embodiments, the ion exchange material and the coating materialAttorney Docket No.: 733PCT601

[0465] form a concentration gradient within the coated ion exchange particles comprising the ion exchange material and the coating material that extends over a thickness selected from the following list: at most 1 nm, at most 10 nm, at most 100 nm, at most 1,000 nm, at most 10,000 nm, or at most 100,000 nm.

[0466]

[0337] In some embodiments, coating thickness may be measured by any one or more of electron microscopy, optical microscopy, couloscopy, nanoindentation, atomic force microscopy, and X-ray fluorescence. In some embodiments, coating thickness may be inferred or extrapolated from data obtained according to an analytical method that indicates the bulk composition of the coated ion exchange particle, or the ion exchange material that further comprises the coating material. In some embodiments, coating thickness may be inferred by differential analysis of data obtained by analysis of ion exchange material that further comprises a coating material and data obtained by analysis ion exchange material that does not further comprise a coating material. In some embodiments, coating thickness may be inferred by differential analysis of data obtained by analysis of one or more coated ion exchange particles and data obtained by analysis of one or more uncoated ion exchange particles.

[0467]

[0338] In some embodiments, the ion exchange material is synthesized by a method selected from the following list: hydrothermal, solvothermal, sol-gel, solid state, molten salt flux, ion exchange, microwave, ball milling, precipitation, or vapor deposition. In some embodiments, the ion exchange material is synthesized by a method selected from the following list: hydrothermal, solid state, or microwave.

[0468]

[0339] In some embodiments, a coating material is deposited to form a coating by a method selected from the following list: chemical vapor deposition, atomic layer deposition, physical vapor deposition, hydrothermal, solvothermal, sol-gel, solid state, molten salt flux, ion exchange, microwave, wet impregnation, precipitation, titration, aging, ball milling, or combinations thereof. In some embodiments, the coating material is deposited to form a coating by a method selected from the following list: chemical vapor deposition, hydrothermal, titration, solvothermal, wet impregnation, sol-gel, precipitation, microwave, or combinations thereof.

[0469]

[0340] In some embodiments, a coating material is deposited to form a coating with physical characteristics selected from the following list: crystalline, amorphous, full coverage, partial coverage, uniform, non-uniform, or combinations thereof.

[0470]

[0341] In some embodiments, multiple coating materials are deposited to form multiple coatings on the ion exchange material in an arrangement selected from the following list: concentric, patchwork, or combinations thereof.Attorney Docket No.: 733PCT601

[0471] Process of extracting lithium from a liquid resource

[0472]

[0342] In one aspect described herein, is a process for lithium extraction from a liquid resource comprising treating an ion exchange material (lithium-selective ion exchange material) alternately with acid, brine, and optionally other solutions, in a configuration where the beads move in the net opposite direction to the acid, brine, and optionally other solutions, thereby producing a lithium-enriched solution from the liquid resource. In one embodiment, the process comprises: (a) treating the ion exchange material with acid under conditions suitable to absorb hydrogen to generate hydrogen-enriched beads and release lithium to generate a lithium-enriched solution; (b) optionally, washing the hydrogen-enriched ion exchange material with water to generate a hydrogen-enriched ion exchange material substantially free of residual acid; (c) treating the hydrogen-enriched ion exchange material with the liquid resource under conditions suitable to absorb lithium to generate a lithium-enriched ion exchange material; (d) optionally, washing the lithium-enriched ion exchange material with water to generate a lithium-enriched ion exchange material substantially free of liquid resource; and (e) repeating the cycle to produce a lithium-enriched solution from the liquid resource.

[0473]

[0343] In an aspect, disclosed herein are compositions for extracting lithium from a liquid resource using a lithium-selective ion exchange material. In some embodiments, this extraction is achieved through the reversible exchange of hydrogen and lithium. In some embodiments, the process begins by treating the lithium-selective ion exchange material with an acid, which releases lithium and results in a protonated lithium-selective ion exchange material. In some embodiments, subsequent lithium extraction cycles are then performed. In some embodiments, each cycle involves contacting the protonated lithium-selective ion exchange material with a liquid resource, allowing it to absorb lithium and produce a lithium-enriched lithium-selective ion exchange material. In some embodiments, this lithium-enriched material is then treated with an acid eluent solution, yielding a synthetic lithium solution and regenerating the protonated lithium-selective ion exchange material, ready for further extraction cycles.

[0474]

[0344] Table 1 summarizes exemplary embodiments of lithium extraction by ion exchange. In the nonlimiting exemplary embodiments, these are characterized by: the release of lithium upon contact of the lithium-selective ion exchange material with an acid to from a protonated lithiumselective ion exchange material, the uptake of lithium upon contacting the protonated lithiumselective ion exchange material with a liquid resource, allowing it to absorb lithium and produce a lithium-enriched lithium-selective ion exchange material. The release of lithium upon contacting said lithium-enriched lithium-selective ion exchange material with an acid.Attorney Docket No.: 733PCT601

[0475]

[0345] In some embodiments, the process of extracting lithium occurs by contacting solutions described above with an ion exchange material occurs within one or more of the devices for lithium extraction disclosed herein.

[0476]

[0346] In one aspect described herein, is a process for lithium extraction from a liquid resource comprising treating ion exchange material alternately with acid, brine, and optionally other solutions, in a configuration where the ion exchange material moves in the net opposite direction to the acid, brine, and optionally other solutions, thereby producing a lithium-enriched solution from the liquid resource. In one aspect described herein, is a process for lithium extraction from a liquid resource comprising treating ion exchange material alternately with acid, the liquid resource, and optionally other solutions, in a configuration where the ion exchange material moves in the net opposite direction to the acid, liquid resource, and optionally other solutions, thereby producing a lithium-enriched solution from the liquid resource. In one aspect described herein, is a process for lithium extraction from a liquid resource comprising treating ion exchange material alternately with acid, brine, and optionally other solutions, in a configuration where the ion exchange material moves in the net opposite direction to the acid, brine, and optionally other solutions, thereby producing a lithium-enriched solution from the brine. In one embodiment, the process comprises: (a) treating the ion exchange material with acid under conditions suitable to absorb hydrogen to generate hydrogen-enriched material and release lithium to generate a lithium-enriched solution; (b) optionally, washing the hydrogen-enriched material with water to generate hydrogen-enriched material substantially free of residual acid; (c) treating the hydrogen-enriched material with the liquid resource under conditions suitable to absorb lithium to generate lithium-enriched material; (d) optionally, washing the lithium-enriched material with water to generate lithium-enriched beads substantially free of liquid resource; and (e) repeating the cycle to produce a lithium-enriched solution from the liquid resource.

[0477]

[0347] In one embodiment, the ion exchange material comprises ion exchange particles that reversibly exchange lithium and hydrogen and a structural matrix material, and having a pore network. In one embodiment, the liquid resource comprises a natural brine, a dissolve salt flat, a concentrated brine, a processed brine, a filtered brine, a liquid from an ion exchange process, a liquid from a solvent extraction process, a synthetic brine, leachate from ores, leachate from minerals, leachate from clays leachate from recycled products, leachate from recycled materials, or combinations thereof.

[0478]

[0348] In some embodiments herein, is a process for lithium extraction from a liquid resource comprising treating an ion exchange material alternately with acid, brine, and optionally otherAttorney Docket No.: 733PCT601

[0479] solutions, in a configuration where the material move in the net opposite direction to the acid, brine, and optionally other solutions, thereby producing a lithium-enriched solution from the liquid resource, wherein the process comprises: a) treating the an ion exchange material with acid under conditions suitable to absorb hydrogen to generate hydrogen-enriched material and release lithium to generate a lithium-enriched solution; b) optionally, washing the hydrogen-enriched material with water to generate hydrogen-enriched beads substantially free of residual acid; c) treating the hydrogen-enriched beads with the liquid resource under conditions suitable to absorb lithium to generate lithium-enriched beads; d) optionally, washing the lithium-enriched beads with water to generate lithium-enriched beads substantially free of liquid resource; and e) repeating the cycle to produce a lithium-enriched solution from the liquid resource.

[0480]

[0349] In one aspect described herein, is a process for lithium extraction from a liquid resource comprising treating ion exchange particles alternately with the liquid resource, washing fluid, and acid, in a system for the extraction of lithium ions from a liquid resource, comprising: a. an ion exchange material; b. a ion exchange vessel; and c. a pH modulating setup for increasing the pH of the liquid resource in the system.

[0481]

[0350] In one aspect described herein, is a process for lithium extraction from a liquid resource comprising treating ion exchange particles alternately with the liquid resource, a washing fluid, and an acid solution, with a system for the extraction of lithium ions from a liquid resource, comprising a stirred rank reactor, an ion exchange material, a pH modulating setup for increasing the pH of the liquid resource in the ion exchange vessel, and a compartment for containing the ion exchange material in the ion exchange vessel while allowing for removal of liquid resource, washing fluid, and acid solutions from the ion exchange vessel.

[0482] Treatment of the liquid resource

[0483]

[0351] An aspect of the disclosure herein is a process for the extraction of lithium ions from a liquid resource, comprising: a) contacting an ion exchange material with the liquid resource; and b) increasing the pH of the liquid resource before contact with the ion exchange material, during contact with the ion exchange material, after contact with the ion exchange material and combinations thereof.

[0484]

[0352] In some embodiments, the pH of the liquid resource is adjusted before, during and / or after contact with the lithium-selective ion exchange material to maintain the pH in range that is suitable for lithium uptake.

[0485]

[0353] To control the pH of the brine and maintain the pH in a range that is suitable for lithium uptake in an ion exchange column, bases such as NaOH, Ca(OH)2, CaO, KOH, or NH3 areAttorney Docket No.: 733PCT601

[0486] optionally added to the brine as solids, aqueous solutions, or in other forms. For brines that contain divalent ions such as Mg, Ca, Sr, or Ba, addition of base to the brine can cause precipitation of solids, such as Mg(0H)2 or Ca(0H)2, which can cause problems for the ion exchange reaction. These precipitates cause problems in at least three ways. First, precipitation can remove base from solution, leaving less base available in solution to neutralize protons and maintain pH in a suitable range for lithium uptake in the ion exchange column. Second, precipitates that form due to base addition can clog the ion exchange column, including clogging the surfaces and pores of an ion exchange material and the voids between an ion exchange material. This clogging can prevent lithium from entering the beads and being absorbed by the ion exchange material. The clogging can also cause large pressure heads in the column. Third, precipitates in the column dissolve during acid elution and thereby contaminate the lithium concentrate produced by the ion exchange system. For an ion exchange material to absorb lithium from brine, an ideal pH range for the brine is optionally 5 to 7, a preferred pH range is optionally 4 to 8, and an acceptable pH range is optionally 1 to 9. In one embodiment, an pH range for the brine is optionally about 1 to about 14, about 2 to about 13, about 3 to about 12, about 4 to about 12, about 4.5 to about 11, about 5 to about 10, about 5 to about 9, about 2 to about 5, about 2 to about 4, about 2 to about 3, about 3 to about 8, about 3 to about 7, about 3 to about 6, about 3 to about 5, about 3 to about 4, about 4 to about 10, about 4 to about 9, about 4 to about 8, about 4 to about 7, about 4 to about 6, about 4 to about 5, about 5 to about 6, about 5 to about 7, about 5 to about 8, about 6 to about 7, about 6 to about 8, or about 7 to about 8.

[0487]

[0354] In one embodiment, the liquid resource is subjected to treatment prior to ion exchange. In some embodiments, said treatment comprises filtration, gravity sedimentation, centrifugal sedimentation, magnetic fields, other methods of solid-liquid separation, or combinations thereof. In some embodiments, precipitated metals are removed from the brine using a filter. In some embodiments, the filter is a belt filter, plate-and-frame filter press, pressure vessel containing filter elements, rotary drum filter, rotary disc filter, cartridge filter, a centrifugal filter with a fixed or moving bed, a metal screen, a perforated basket centrifuge, a three-point centrifuge, a peeler type centrifuge, or a pusher centrifuge. In some embodiments, the filter may use a scroll or a vibrating device. In some embodiments, the filter is horizontal, vertical, or may use a siphon.

[0488]

[0355] In some embodiments, a filter cake is prevented, limited, or removed by using gravity, centrifugal force, an electric field, vibration, brushes, liquid jets, scrapers, intermittent reverse flow, vibration, crow-flow filtration, or pumping suspensions across the surface of the filter. In some embodiments, the precipitated metals and a liquid is moved tangentially to the filter toAttorney Docket No.: 733PCT601

[0489] limit cake growth. In some embodiments, gravitational, magnetic, centrifugal sedimentation, or other means of solid-liquid separation are used before, during, or after filtering to prevent cake formation.

[0490]

[0356] In some embodiments, a filter comprises a screen, a metal screen, a sieve, a sieve bend, a bent sieve, a high frequency electromagnetic screen, a resonance screen, or combinations thereof. In some embodiments, one or more particle traps are a solid-liquid separation apparatus.

[0491]

[0357] In some embodiments, one or more solid-liquid separation apparatuses are used in series or parallel. In some embodiments, a dilute slurry is removed from the tank, transferred to an external solid-liquid separation apparatus, and separated into a concentrated slurry and a solution with low or no suspended solids. In some embodiments, the concentrated slurry is returned to the tank or transferred to a different tank. In some embodiments, precipitate metals are transferred from a brine tank to another brine tank, from an acid tank to another acid tank, from a washing tank to another washing tank, from a brine tank to a washing tank, from a washing tank to an acid tank, from an acid tank to a washing tank, or from an acid tank to a brine tank.

[0492]

[0358] In some embodiments, solid-liquid separation apparatuses may use gravitational sedimentation. In some embodiments, solid-liquid separation apparatuses may include a settling tank, a thickener, a clarifier, a gravity thickener. In some embodiments, solid-liquid separation apparatuses are operated in batch mode, semi-batch mode, semi-continuous mode, or continuous mode. In some embodiments, solid-liquid separation apparatuses include a circular basin thickener with slurry entering through a central inlet such that the slurry is dispersed into the thickener with one or more raking components that rotate and concentrate the ion exchange particles into a zone where the particles can leave through the bottom of the thickener.

[0493]

[0359] In some embodiments, solid-liquid separation apparatuses include a deep cone, a deep cone tank, a deep cone compression tank, or a tank wherein the slurry is compacted by weight. In some embodiments, solid-liquid separation apparatuses include a tray thickener with a series of thickeners oriented vertically with a center axle and raking components. In some embodiments, solid-liquid separation apparatuses include a lamella type thickener with inclined plates or tubes that are smooth, flat, rough, or cormgated. In some embodiments, solid-liquid separation apparatuses include a gravity clarifier that is a rectangular basin with feed at one end and overflow at the opposite end optionally with paddles and / or a chain mechanism to move particles. In some embodiments, the solid-liquid separation apparatuses are a particle trap.

[0494]

[0360] In some embodiments, the solid-liquid separation apparatuses use centrifugal sedimentation. In some embodiments, solid-liquid separation apparatuses may include a tubular centrifuge, a multi-chamber centrifuge, a conical basket centrifuge, a scroll-type centrifuge, aAttorney Docket No.: 733PCT601

[0495] sedimenting centrifuge, or a disc centrifuge. In some embodiments, precipitated metals are discharged continuously or intermittently from the centrifuge. In some embodiments, the solidliquid separation apparatus is a hydrocyclone. In some embodiments, solid-liquid separation apparatus is an array of hydrocyclones or centrifuges in series and / or in parallel. In some embodiments, sumps are used to reslurry the precipitated metals. In some embodiments, the hydrocyclones have multiple feed points. In some embodiments, a hydrocyclone is used upside down. In some embodiments, liquid is injected near the apex of the cone of a hydrocyclone to improve sharpness of cut. In some embodiments, a weir rotates in the center of the particle trap with a feed of slurried precipitated metals entering near the middle of the apparatus, and precipitated metals get trapped at the bottom and center of the apparatus due to a “teacup effect”.

[0496] Treatment of the lithium-selective ion exchange material with chemical additives

[0361] In an aspect, described herein is a system for contacting the lithium-selective ion exchange material with chemical additives. In some embodiments, a system for extracting lithium from a liquid resource comprises the system for contacting the lithium-selective ion exchange material with chemical additives. In some embodiments, a method for extracting lithium from a liquid resource comprises contacting the lithium-selective ion exchange material with chemical additives. In some embodiments, a method for extracting lithium from a liquid resource comprises contacting the liquid resource, the wash solution, or the acidic solution with chemical additives prior to contacting the liquid resource, the wash solution, or the acidic solution with the lithium-selective ion exchange material. In some embodiments, the process of producing lithium by ion exchange makes use of said system to add chemical additives. In some embodiments, the lithium-selective ion exchange material is contacted with a chemical additive by directly treating the lithium-selective ion exchange material with the chemical additive. In some embodiments, the lithium-selective ion exchange material is contacted with a chemical additive by treating the liquid resource with one or more chemical additives, and then contacting said liquid resource containing chemical additives with the lithium-selective ion exchange material to absorb the lithium in the liquid resource. In some embodiments, the lithium-selective ion exchange material is contacted with a chemical additive by treating the process water with one or more chemical additives, and then contacting said process water containing chemical additives with the lithium-selective ion exchange material to wash the lithium-selective ion exchange material. In some embodiments, the lithium-selective ion exchange material is contacted with a chemical additive by treating an acid with one or more chemical additives, andAttorney Docket No.: 733PCT601

[0497] then contacting said acid with the lithium-selective ion exchange material to elute the lithium. In some embodiments, the lithium-selective ion exchange material is contacted with a chemical additive by treating a base with one or more chemical additives, and then contacting said base with the lithium-selective ion exchange material to adjust the pH of the liquid resource.

[0498]

[0362] In some embodiments, the lithium-selective ion exchange material is contacted with one or more chemical additives before lithium is absorbed from a liquid resource thereby. In some embodiments, the lithium-selective ion exchange material is contacted with one or more chemical additives while lithium is absorbed from a liquid resource thereby. In some embodiments, the lithium-selective ion exchange material is contacted with one or more chemical additives after lithium is absorbed from a liquid resource thereby. In some embodiments, the lithium-selective ion exchange material is contacted with one or more chemical additives before entrained liquid resource is removed from the lithium-selective ion exchange material by washing, direct application, or other methods. In some embodiments, the lithium-selective ion exchange material is contacted with one or more chemical additives while entrained liquid resource is removed from the lithium-selective ion exchange material by washing or other methods. In some embodiments, the lithium-selective ion exchange material is contacted with one or more chemical additives after entrained liquid resource is removed from the lithium-selective ion exchange material by washing or other methods. In some embodiments, the liquid resource is removed from the lithium-selective ion exchange material by treatment with a stream comprising one or more chemical additives. In some embodiments, said stream comprising one or more chemical additives comprises water, liquid resource, an aqueous solution, or a gas. In some embodiments, the lithium-selective ion exchange material is contacted with one or more chemical additives before said lithium-selective ion exchange material is contacted with an acid to elute the lithium. In some embodiments, the lithiumselective ion exchange material is contacted with one or more chemical additives while said lithium-selective ion exchange material is contacted with an acid to elute the lithium. In some embodiments, the lithium-selective ion exchange material is contacted with one or more chemical additives after said lithium-selective ion exchange material is contacted with an acid to elute the lithium. In some embodiments, the lithium-selective ion exchange material is contacted with chemical additives before and after each of steps (lithium absorption, removal of entrained liquid resource, and elution) described above. In some embodiments, the lithium-selective ion exchange material is contacted with chemical additives before and / or after some of each of steps (lithium absorption, removal of entrained liquid resource, and elution) described above.Attorney Docket No.: 733PCT601

[0499]

[0363] In some embodiments, the lithium-selective ion exchange material is contacted with chemical additives during each ion exchange cycle wherein each cycle comprises lithium absorption and lithium elution. In some embodiments, the lithium-selective ion exchange material is contacted with chemical additives during each ion exchange cycle or every other ion exchange cycle wherein each cycle comprises lithium absorption and lithium elution. In some embodiments, the lithium-selective ion exchange material is contacted with chemical additives every second ion exchange cycle wherein each cycle comprises lithium absorption and lithium elution. In some embodiments, the lithium-selective ion exchange material is contacted with chemical additives in even or uneven intervals of ion exchange cycles, wherein each cycle comprises lithium absorption and lithium elution.

[0500]

[0364] In some embodiments, the l...

Claims

1. Attorney Docket No.: 733PCT601CLAIMS WHAT IS CLAIMED IS:

1. A lithium-selective ion exchange material composition, said composition comprising:a) particles of a mixed metal oxide,i) wherein said mixed metal oxide comprises lithium, oxygen, and a transition metal, ii) wherein the transition metal is selected from titanium and manganese, and iii) wherein the molar ratio of lithium to transition metal is from 0.25:1 to 4:1;b) one or more optional matrix materials,i) wherein the particles of a mixed metal oxide are coated by, embedded in, adhered to, or otherwise supported by the one or more matrix materials;c) wherein the lithium-selective ion exchange material composition is in the form of particles, wherein the particles exhibit the following properties:i) a specific pore volume of 0.01 ml / g to 0.25 ml / g, as determined by N2 physisorption, ii) a specific surface area of 1 m2 / g to 100 m2 / g, as determined by the Brunauer-Emmett- Teller (BET) method using N2 physisorption data,iii) a dlO larger than 1 pm, andiv) a d90 smaller than 1 mm.

2. The composition of claim 1, wherein the transition metal is titanium.

3. The composition of claim 1, wherein the transition metal is manganese.

4. The composition of any of the claims 1 to 3, wherein the molar ratio of lithium to transition metal from 0.25: 1 to 1: 1.

5. The composition of any one of claims 1 to 3, wherein the molar ratio of lithium to transition metal ranges from 1:1 to 1:2.

6. The composition of any one of claims 1 to 3, wherein the molar ratio of lithium to transition metal ranges from 1:2 to 1:4.

7. The composition of any one of claims 1 to 3, wherein the molar ratio of lithium to transition metal is about 2:1, about 0.8:1, about 0.5:1, about 1:1, or about 3:1.

8. The composition of claims 1 to 3, wherein the transition metal is titanium, and wherein the molar ratio of lithium to titanium is about 2:1, about 0.8:1, or about 1:1.

9. The composition of claims 1 to 3, wherein the transition metal is manganese, and wherein the molar ratio of lithium to manganese is about 2: 1, about 0.8:1, or about 1:1.

10. The composition of any one of claims 1 to 9, wherein the mixed metal oxide is a lithiumselective ion exchange material.207326623476v2Attorney Docket No.: 733PCT60111. The composition of claim 10, wherein the lithium-selective ion exchange material is selected from: LiMnPO4, Li2TiO3, Li2Ti2O5, Li2MnO3, Li2Mn2O5, L TisO^, Li4Mn5O12, LiTi2O4, LiMn2C>4, Li1.6Mn1.6O4, compounds thereof, nonstoichiometric compounds thereof, modifications thereof, solid solutions thereof, or a combination thereof.

12. The composition of any one of claims 1 to 11, wherein the particles of the mixed metal oxide are at least partially coated by, embedded in, adhered to, or otherwise supported by a first one or more matrix materials.

13. The composition of any one of claims 1 to 12, wherein the particles of the mixed metal oxide are at least partially coated by, embedded in, adhered to, or otherwise supported by a second one or more matrix materials.

14. The composition of any one of claims 1 to 13, wherein said one or more matrix materials comprises TiO2, ZrO2, SiO2, Al2O3, polyvinylidene fluoride, polyvinyl fluoride, polyvinyl chloride, polyvinylidene chloride, a chloro-polymer, a fluoro-polymer, a fluoro-chloro- polymer, polyethylene, polypropylene, polyphenylene sulfide, polytetrafluoroethylene, sulfonated polytetrafluoroethylene, polystyrene, polymethyl methacrylate, polydivinylbenzene, polybutadiene, a sulfonated polymer, a carboxylated polymer, polyacrylonitrile, perfluoro-3,6-dioxa-4-methyl-7-octene-sulfonic acid, dioxa-4-methyl-7- octene-sulfonic acid, copolymers thereof, or combinations thereof.

15. The composition of any one of claims 1 to 14, wherein said one or more matrix materials comprises polyvinylidene fluoride, polyvinyl fluoride, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polyphenylene sulfide, polytetrafluoroethylene, sulfonated polytetrafluoroethylene, polystyrene, polymethyl methacrylate, polydivinylbenzene, polybutadiene, polyacrylonitrile, perfluoro-3,6-dioxa-4-methyl-7- octene-sulfonic acid, dioxa-4-methyl-7-octene-sulfonic acid, copolymers thereof, or combinations thereof.

16. The composition of any one of claims 1 to 15 wherein said one or more matrix materials comprises polyvinylidene fluoride, polyvinyl fluoride, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polyphenylene sulfide, polystyrene, polybutadiene, copolymers thereof, or combinations thereof.

17. The composition of any one of claims 1 to 14, wherein said one or more matrix materials comprises TiO2, ZrO2, SiO2, Al2O3, solid solutions thereof, or combinations thereof.

18. The composition of any one of claims 1 to 13, wherein:208326623476v2Attorney Docket No.: 733PCT601a) the first matrix material is selected from: TiO2, ZrO2, SiO2, Al2O3, solid solutions thereof, or mixed oxides thereof, or combinations thereof;b) the second matrix material is selected from: polyvinylidene fluoride, polyvinyl fluoride, polyvinyl chloride, polyvinylidene chloride, a chloro-polymer, a fluoro-polymer, a fluorochloro-polymer, polyethylene, polypropylene, polyphenylene sulfide, polytetrafluoroethylene, sulfonated polytetrafluoroethylene, polystyrene, polydivinylbenzene, polybutadiene, a sulfonated polymer, a carboxylated polymer, polyacrylonitrile, perfluoro-3,6-dioxa-4-methyl-7-octene-sulfonic acid, copolymers thereof, or combinations thereof.dioxa-4-methyl-7-octene-sulfonic acid, copolymers thereof, or combinations thereof.

19. The composition of any one of claims 1 to 13, wherein:a) the first matrix material is selected from: polyvinylidene fluoride, polyvinyl fluoride, polyvinyl chloride, polyvinylidene chloride, a chloro-polymer, a fluoro-polymer, a fluoro- chloro-polymer, polyethylene, polypropylene, polyphenylene sulfide, polytetrafluoroethylene, sulfonated polytetrafluoroethylene, polystyrene, polydivinylbenzene, polybutadiene, a sulfonated polymer, a carboxylated polymer, polyacrylonitrile, perfluoro-3,6-dioxa-4-methyl-7-octene-sulfonic acid, copolymers thereof, or combinations thereof.dioxa-4-methyl-7-octene-sulfonic acid, copolymers thereof, or combinations thereof;b) the second matrix material is selected from: TiCL, ZrO2, SiCh, AI2O3, solid solutions thereof, or mixed oxides thereof, or combinations thereof.

20. The composition of any one of claims 1 to 19, wherein percent weight of the one or more matrix materials in the composition is from about 1 to 40 %.

21. The composition of any one of claims 1 to 20, wherein percent weight of the one or more matrix materials in the composition is from about 5 to 30 %.

22. The composition of any one of claims 1 to 21, wherein percent weight of the one or more matrix materials in the composition is from about 10 to 25 %.

23. The composition of any one of claims 1 to 22, wherein the pore volume of the lithiumselective ion exchange material composition is at least about 0.001 mL / g, at least about 0.005 mL / g, at least about 0.01 mL / g, at least about 0.05 mL / g, at least about 0.1 mL / g, at least about 0.2 mL / g, or at least about 0.3 mL / g.

24. The composition of any one of claims 1 to 22, wherein the pore volume of the lithiumselective ion exchange material composition is from about 0.01 to 0.3 mL / g.209326623476v2Attorney Docket No.: 733PCT60125. The composition of any one of claims 1 to 22, wherein the pore volume of the lithiumselective ion exchange material composition is from about 0.05 to 0.2 mL / g.

26. The composition of any one of claims 1 to 25, wherein the specific surface area of the lithium-selective ion exchange material composition is at least about 1 m2 / g, at least about 5 m2 / g, at least about 10 m2 / g, at least about 25 m2 / g, at least about 50 m2 / g, or at least about 100 m2 / g.

27. The composition of any one of claims 1 to 25, wherein the specific surface area of the lithium-selective ion exchange material composition is from about 1 to 100 m2 / g.

28. The composition of any one of claims 1 to 25, wherein the specific surface area of the lithium-selective ion exchange material composition is from about 20 to 70 m2 / g.

29. The composition of any one of claims 1 to 28, wherein the characteristic diameter of 95 wt% of the particles of lithium-selective ion exchange material composition is from about 100 to 200 pm, about 150 to 200 pm, about 200 to 300 pm, about 250 to 300, pm, about 100 to 200 pm, about 5 to 100 pm, about 25 to 100 pm, about 45 to 100 pm, about 60 to 100 pm, about 5 to 150 pm, about 10 to 150 pm, about 25 to 150 pm, about 45 to 150 pm, or about 60 to 150 pm.

30. The composition of any one of claims 1 to 28, wherein the characteristic diameter of 90 wt% of the particles of the lithium-selective ion exchange material composition is from about 100 to 200 pm, about 150 to 200 pm, about 200 to 300 pm, about 250 to 300, pm, about 100 to 200 pm, about 5 to 100 pm, about 25 to 100 pm, about 45 to 100 pm, about 60 to 100 pm, about 5 to 150 pm, about 10 to 150 pm, about 25 to 150 pm, about 45 to 150 pm, or about 60 to 150 pm.

31. The composition of any one of claims 1 to 28, wherein the ds of the particles of the lithiumselective ion exchange material composition is about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 60 pm, about 75 pm, or about 100 pm.

32. The composition of any one of claims 1 to 28, wherein the ds of the particles of the lithiumselective ion exchange material composition is about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 60 pm, about 75 pm, or about 100 pm.

33. The composition of any one of claims 1 to 28, wherein the dio of the particles of the lithiumselective ion exchange material composition is about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 60 pm, about 75 pm, or about 100 pm.210326623476v2Attorney Docket No.: 733PCT60134. The composition of any one of claims 1 to 28, wherein the dyo of the particles of the lithiumselective ion exchange material composition is about 75 pm, about 100 pm, about 150 pm, about 200 pm, or about 300 pm.

35. The composition of any one of claims 1 to 28, wherein the dys of the particles of the lithiumselective ion exchange material composition is about 75 pm, about 100 pm, about 150 pm, about 200 pm, or about 300 pm.

36. The composition of any one of claims 1 to 28, wherein the dy? of the particles of the lithiumselective ion exchange material composition is about 75 pm, about 100 pm, about 150 pm, about 200 pm, or about 300 pm.

37. The composition of any one of claims 1 to 36, wherein the composition exhibits a lithium leach percent of at least about 60%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 99%.

38. The composition of any one of claims 1 to 36, wherein the composition exhibits a lithium extraction percent of at least about 50%, at least about 60%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 99%.

39. The composition of any one of claims 1 to 38, wherein the source of lithium is a low grade brine with a lithium concentration of under 2,500 mg / L of lithium.

40. The composition of any one of claims 1 to 39, wherein the source of lithium is a low grade brine with a lithium concentration of under 2,000 mg / L of lithium.

41. The composition of any one of claims 1 to 40, wherein the lithium concentration of under 1,000 mg / L of lithium.

42. The composition of any one of claims 1 to 41, wherein the lithium concentration of under 500 mg / L of lithium.

43. The composition of any one of claims 1 to 42, wherein the lithium concentration of under 100 mg / L of lithium.

44. The composition of any one of claims 1 to 43, wherein the settling velocity the lithiumselective ion exchange material composition in water at room temperature is at least 0.1 cm / min, at least 1 cm / min, at least 5 cm I min, at least 10 cm / min, at least 50 cm / min, at least 100 cm / min, at least 1,000 cm / min or at least 1,500 cm / min.

45. The composition of any one of claims 1 to 43, wherein the settling velocity the lithiumselective ion exchange material composition in water at room temperature is from 0.1 to 1,500 cm / min.211326623476v2Attorney Docket No.: 733PCT60146. The composition of any one of claims 1 to 43, wherein the settling velocity the lithiumselective ion exchange material composition in water at room temperature is from 5 to 100 cm I min.

47. The composition of claim any one of claims 1 to 46, wherein the lithium-selective ion exchange material composition has the following hydrodynamic characteristics:i) the pressure drop of water flowing through a packed bed of said composition at most 50 psi / cm as water flows though the bed at a superficial velocity of 5 cm / min; and ii) the settling velocity of said particles in water at room temperature at least 0.1 cm / min.

48. The composition of any one of claims 1 to 47, wherein a packed bed said of composition exhibits a pressure drop of at most 1 psi / cm, 3 psi / cm, 5 psi / cm, 10 psi / cm, 20 psi / cm, 40 psi / cm, 80 psi / cm, or 100 psi / cm, as water flows through the bed at a superficial velocity of 0.5 cm / min.

49. The composition of any one of claims 1 to 47, wherein a packed bed of said composition exhibits a pressure drop of at most 1 psi / cm, 3 psi / cm, 5 psi / cm, 10 psi / cm, 20 psi / cm, 40 psi / cm, 80 psi / cm, or 100 psi / cm, as water flows through the bed at a superficial velocity of 1 cm / min.

50. The composition of any one of claims 1 to 47, wherein a packed bed of said composition exhibits a pressure drop of at most 1 psi / cm, 3 psi / cm, 5 psi / cm, 10 psi / cm, 20 psi / cm, 40 psi / cm, 80 psi / cm, or 100 psi / cm, as water flows through the bed at a superficial velocity of 5 cm / min.

51. The composition of any one of claims 1 to 47, wherein a packed bed of said composition exhibits a pressure drop of at most 1 psi / cm, 3 psi / cm, 5 psi / cm, 10 psi / cm, 20 psi / cm, 40 psi / cm, 80 psi / cm, or 100 psi / cm, as water flows through the bed at a superficial velocity of 10 cm / min.

52. The composition of any one of claims 1 to 51, wherein the mixed metal oxide is generated from a metal precursor and a lithium salt precursor.

53. The composition of claim 52, wherein the lithium salt precursor is selected from: lithium sulfate, lithium carbonate, lithium nitrate, lithium phosphate, lithium hydroxide, lithium chloride, hydrates thereof, or combinations thereof.

54. The composition of claim 52 or 53, wherein the metal precursor is selected from: titanium dioxide, titanium alkoxides, titanium chloride, manganese dioxide, manganese oxide, manganese carbonate, manganese acetate, manganese hydroxide, manganese nitrate,212326623476v2Attorney Docket No.: 733PCT601manganese sulfate, manganese phosphate, NixMnyCo1-x-y(OH)2, NixMnyAl1-x-y(OH)2, solid solutions thereof, or combinations thereof.

55. The composition of any one of claims 52 to 54, wherein the metal precursor has a d5particle size of about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm, or about 1 mm.

56. The composition of any one of claims 52 to 54, wherein the metal precursor has a dio particle size of about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 pm, or about 1 mm.

57. The composition of any one of claims 52 to 54, wherein the metal precursor has a ds>o particle size of about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 pm, or about 1 mm.

58. The composition of any one of claims 52 to 54, wherein the metal precursor has a d95particle size of about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm, or about 1 mm.

59. The composition of any one of claims 52 to 54, wherein the characteristic diameter of 95 wt% of the particles of the metal precursor is from about 100 to 200 pm, about 150 to 200 pm, about 200 to 300 pm, about 250 to 300, pm, about 100 to 200 pm, about 5 to 100 pm, about 1 to 100 pm, about 10 to 100 pm, about 25 to 100 pm, about 45 to 100 pm, about 60 to 100 pm, about 5 to 150 pm, about 10 to 150 pm, about 25 to 150 pm, about 45 to 150 pm, about 50 to 150 pm, about 55 to 140 pm, or about 60 to 150 pm.

60. A process for manufacturing a lithium-selective ion exchange material composition, the process comprising:(a) generating the mixed metal oxide, wherein the mixed metal oxide is generated by:(i) contacting a lithium salt precursor with a metal precursor to generate a synthesis mixture, and(ii) heating said synthesis mixture to form the mixed metal oxide;(b) optionally embedding the mixed metal oxide in a matrix material(c) selectively sizing the mixed metal oxide, the metal precursor, the lithium salt precursor, the matrix material, the lithium-selective ion exchange material composition, or any combination thereof;wherein the lithium-selective ion exchange material composition is in the form of particles exhibiting the following properties:1) the pore volume is from 0.001 ml / g to 0.1 ml / g;213326623476v2Attorney Docket No.: 733PCT6012) the specific surface area is from 1 m2 / g to 100 m2 / g;3) the particle size of 99% of the composition is from about 5 to 500 pm.

61. The process of claim 60, wherein step (ii) occurs in a pusher kiln, a roller hearth kiln, a rotary kiln, a rotary furnace, a muffle furnace, a batch furnace, or a continuous furnace.

62. The process of claims 60 or 61, wherein the temperature in step (ii) is controlled to be in the range of: from about 470 K to about 480 K, from about 480 K to about 490 K, from about 490 K to about 500 K, from about 500 K to about 510 K, from about 510 K to about 520 K, from about 520 K to about 530 K, from about 530 K to about 540 K, from about 540 K to about 550 K, from about 550 K to about 560 K, from about 560 K to about 570 K, from about 570 K to about 580 K, from about 580 K to about 590 K, from about 590 K to about 600 K, from about 600 K to about 610 K, from about 610 K to about 620 K, from about 620 K to about 630 K, from about 630 K to about 640 K, from about 640 K to about 650 K, from about 650 K to about 660 K, from about 660 K to about 670 K, from about 670 K to about 680 K, from about 680 K to about 690 K, from about 690 K to about 700 K, from about 700 K to about 710 K, from about 710 K to about 720 K, from about 720 K to about 730 K, from about 730 K to about 740 K, from about 740 K to about 750 K, from about 750 K to about 760 K, from about 760 K to about 770 K, from about 770 K to about 780 K, from about 780 K to about 790 K, from about 790 K to about 800 K, from about 800 K to about 810 K, from about 810 K to about 820 K, from about 820 K to about 830 K, from about 830 K to about 840 K, from about 840 K to about 850 K, from about 850 K to about 860 K, from about 860 K to about 870 K, from about 870 K to about 880 K, from about 880 K to about 890 K, from about 890 K to about 900 K.

63. The process of any one of claims 60 to 62, wherein the temperature in step (ii) is controlled to be in the range of from about 350 K to about 850 K.

64. The process of any one of claims 60 to 63, wherein the temperature in step (ii) is controlled to be in the range of from about 650 K to about 850 K.

65. The process of any one of claims 60 to 64, wherein the lithium salt precursor is selected from:lithium sulfate, lithium carbonate, lithium nitrate, lithium phosphate, lithium hydroxide, lithium chloride, hydrates thereof, or combinations thereof.

66. The process of any one of claims 60 to 65, wherein the metal precursor is selected from: titanium dioxide, titanium alkoxides, titanium chloride, manganese dioxide, manganese oxide, manganese carbonate, manganese acetate, manganese hydroxide, manganese nitrate,214326623476v2Attorney Docket No.: 733PCT601manganese sulfate, manganese phosphate, NixMnyCo1-x-y(OH)2, NixMnyAl1-x-y(OH)2, solid solutions thereof, or combinations thereof.

67. The process of any one of claims 60 to 66, wherein the metal precursor is produced or refined by chemical, sol-gel, electrolytic, carbothermic, hydrothermal, hydrometallurgical, or pyrometallurgical processes, or a combination thereof.

68. The process of any one of claims 60 to 67, wherein the mixed metal oxide, the lithium salt precursor, the metal precursor, the matrix material, or the lithium-selective ion exchange material composition is sized to have a ds particle size of about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 pm, or about 1 mm.

69. The process of any one of claims 60 to 67, wherein the mixed metal oxide, the lithium salt precursor, the metal precursor, the matrix material, or the lithium-selective ion exchange material composition is sized to have a dio particle size of about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 pm, or about 1 mm.

70. The process of any one of claims 60 to 67, wherein the mixed metal oxide, the lithium salt precursor, the metal precursor, the matrix material, or the lithium-selective ion exchange material composition is sized to have a d<>o particle size of about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 pm, or about 1 mm.

71. The process of any one of claims 60 to 67, wherein the mixed metal oxide, the lithium salt precursor, the metal precursor, the matrix material, or the lithium-selective ion exchange material composition is sized to have a d95 particle size of about 0.1 pm, about 0.5 pm, about 1 pm, about 5 pm, about 10 pm, about 25 pm, about 50 pm, about 75 pm, about 100 pm, about 250 pm, about 500 pm, or about 1 mm.

72. The process of any one of claims 60 to 71, wherein sizing is performed by dry screening, air classification, wet classification, decantation, sieving, screening, sifting, gravity separation, elutriation, centrifugation, settling, clarification, filtering, or combined processes thereof.

73. The process of claim 72, wherein said dry screening comprises one or more sieves, screens, mechanical vibration devices, or other devices designed to retain particles above a minimum size while allowing smaller particles to pass through.

74. The process of claim 72, wherein said air classification comprises one or more devices selected from: gravitational air classifiers, air-jet sieving devices, gravitational inertial air 215326623476v2Attorney Docket No.: 733PCT601classifiers, centrifugal air classifiers, gyrotor air classifiers, cyclones, or combinations thereof.

75. The process of claim 72, wherein said wet classification unit comprises one or more devices selected from: a clarifier, a lamellar clarifier, hydrocyclone, a cyclone, an elutriation device, a reflux classifier, a wet sieve, a wet screening device, a vibratory wet screening device, a decantation device, or combinations thereof.

76. The process of claim 72, wherein set wet classification devices comprises:a) a repulping unit, configured to suspend the particles of the mixed metal oxide, the lithium salt precursor, the metal precursor, the matrix material, or the lithium-selective ion exchange material composition;b) a wet classification device comprising,i) one or more screens configured to retain larger particles of the mixed metal oxide, the lithium salt precursor, the metal precursor, the matrix material, or the lithiumselective ion exchange material composition while allowing smaller particles to pass and be discarded;ii) components designed to efficiently liberate smaller particles, including but not limited to: one or more spraying devices designed to wash the particles, one or more mechanical vibration devices designed to allow efficient washing of the particles, one or more flow distribution devices configured to efficiently direct the particles into the one or more screens, or a combination thereof;c) an optional water recycling unit, configured to recycle at least a portion of the water used for the wet classification process.

77. The process of claims 75 or 76, further comprising drying the wet classified material.

78. The process of 77, wherein said drying is performed in a convection drier, a vacuum drier, or other device designed to remove a liquid from a solid at ambient or elevated temperature.

79. The process of any one of claims 60 to 78, wherein particles rejected by the classification unit are recycled to synthesize the metal precursor.

80. The process of any one of claims 60 to 79, wherein the size of the particles of the mixed metal oxide, the lithium salt precursor, the metal precursor, the matrix material, or the lithium-selective ion exchange material composition is increased prior to sizing.

81. The process of claim 80, wherein the size of the particles is increased by extrusion, casting, pelletizing, tabletizing, pressing, granulating, calendaring, compression molding, thermoforming, sintering, or otherwise treating the particles to form aggregates thereof.216326623476v2Attorney Docket No.: 733PCT60182. The process of any one of claims 60 to 79, wherein the size of the particles of the mixed metal oxide, the lithium salt precursor, the metal precursor, the matrix material, or the lithium-selective ion exchange material composition is reduced prior to sizing.

83. The process of claim 82, wherein the size of the particles is reduced by processing said particles by a method selected from: crushing, grinding, cutting, attrition, milling (including jet milling, cryo milling, ball milling, hammer milling, pin milling, disc milling, roller milling, attrition milling, fluid energy milling, ultrasonic milling, high-shear milling, wet milling, dry milling, bead milling, vibratory milling, planetary ball milling, fluid bed milling, pancake milling, loop milling, ball milling, impact milling, colloid milling, air-jet milling, conical milling), delumping, granulating, self-attrition, shredding, pulverization, micronization, ultrasonic treatment, or other methods of size reduction acting through the forces of impact, shear, compression, combinations, or process integrations thereof.

84. The process of any one of claims 60 to 83, wherein the mixed metal oxide is at least partially coated by, embedded in, adhered to, or otherwise supported by the one or more matrix materials.

85. The process of claim 84, wherein said coating, embedding, adhesion, or support is achieved by a method comprising:i) obtaining a first matrix material precursor,ii) contacting said first matrix material precursor to the mixed metal oxide to obtain a first matrix-particle mixture,iii) optionally treating said matrix-particle mixture to coat, embed, adhere, or otherwise support the mixed metal oxide within a first matrix material;iv) optionally, repeating ii) with a second matrix material precursor to obtain a second matrix-particle mixture and optionally iii) to a to coat, embed, adhere, or otherwise support the mixed metal oxide and first matrix material.

86. The process of claim 84 or 85, wherein the particles of the mixed metal oxide are coated by one of the said one or more matrix materials.

87. The process of claims 84 or 85, wherein the mixed metal oxide is embedded within one or more of said matrix materials.

88. The process of claims 84 or 85, wherein the mixed metal oxide is adhered to one or more of said matrix materials.

89. The process of claims 84 or 85, wherein the mixed metal oxide is supported by one or more of said matrix materials.217326623476v2Attorney Docket No.: 733PCT60190. The process of claims 84 or 85, wherein the mixed metal oxide is coated by the first one or more matrix material, and embedded within the second matrix material.

91. The process of claims 84 or 85, wherein the mixed metal oxide is coated by the first one or more matrix material, and adhered to the second matrix material.

92. The process of claims 84 or 85, wherein the mixed metal oxide is coated by the first one or more matrix material, and supported by the second matrix material.

93. The process of any one of claims 85 to 92 [N - 8] to [N - 1], wherein said first or second matrix material precursors is obtained by mixing a matrix material with a liquid.

94. The process of claim 93, wherein said matrix material dissolves in said liquid to form a solution.

95. The process of claim 93, wherein said matrix material and said liquid form a slurry.

96. The process of any one of claims 93 to 95, wherein said liquid is water or an aqueous solution.

97. The process of any one of claims 93 to 95, wherein said liquid is an organic solvent.

98. The process of claims 97 wherein said organic solvent is selected from: acetone, ethyl acetate, dichloromethane (DCM), N. N-dimethylformamide (DMF), tetrahydrofuran (THF), N, N-dimethylacetamide (DMAc), chloroform, toluene, methyl ethyl ketone (MEK), anisole, mixtures thereof, solutions thereof, or combinations thereof.

99. The process of any one of claims 84 to 98, wherein said first or second matrix-particle mixture is obtained by mixing said first or second matrix material precursor and the mixed metal oxide.

100. The process of claim 99, wherein said mixing is performed in a unit selected from: a blender, a high-speed disperser, an mixing tank, an agitated mixing tank, a multi-shaft mixer, a high-shear mixer, a low-speed mixer, a planetary mixer, a static mixer, an ultrasonic homogenizer, a rotor-stator mixer, a double planetary mixer, a kneader, an extruder, a ribbon blender, a high-pressure homogenizer, a granulator, or a combined process thereof.

101. The process of any one of claims 84 to 100, wherein said first matrix-particle mixture is further processed to form an intermediate composite structure, wherein the processes comprises extrusion, in-line mixing, casting, pelletizing, tabletizing, mixing, blending, compounding, milling, granulation, calendering, injection molding, compression molding, blow molding, thermoforming, rotational molding, coating, laminating, sintering, pressing, drying, devolatilization, filtration, centrifugation, or combinations thereof.218326623476v2Attorney Docket No.: 733PCT601102. The process of claim 101, where said intermediate composite structure is formed by 1) extruding, casting, granulating, or otherwise forming a continuous structure of the matrixparticle mixture, and 2) drying said continuous structure the matrix-particle mixture.

103. The process of claims 101 or 102, where said intermediate composite structure is formed by 1) extruding, pressing, pelletizing, or tabletizing said matrix-particle mixture to form pellets, granules, tablets, or briquettes, and 2) sintering said pellets, granules, tables, or briquettes.

104. The process of any one of claims 101 to 103, wherein said drying or sintering is performed at a controlled temperature, and wherein said temperature is in the range of: from about 70 K to about 80 K, from about 80 K to about 90 K, from about 90 K to about 100 K, from about 100 K to about 110 K, from about 110 K to about 120 K, from about 120 K to about 130 K, from about 130 K to about 140 K, from about 140 K to about 150 K, from about 150 K to about 160 K, from about 160 K to about 170 K, from about 170 K to about 180 K, from about 180 K to about 190 K, from about 190 K to about 200 K, from about 200 K to about 210 K, from about 210 K to about 220 K, from about 220 K to about 230 K, from about 230 K to about 240 K, from about 240 K to about 250 K, from about 250 K to about 260 K, from about 260 K to about 270 K, from about 270 K to about 280 K, from about 280 K to about 290 K, from about 290 K to about 300 K, from about 300 K to about 310 K, from about 310 K to about 320 K, from about 320 K to about 330 K, from about 330 K to about 340 K, from about 340 K to about 350 K, from about 350 K to about 360 K, from about 360 K to about 370 K, from about 370 K to about 380 K.

105. The process of any one of claims 101 to 104, where said intermediate composite structure is formed by two processes selected from: extruding, pressing, pelletizing, sintering, or tabletizing said matrix-particle mixture to form a continuous structure.

106. The process of any one of claims 101 to 105, wherein said intermediate composite structure is in the form of pellets, beads, tablets, briquettes, granules, powder, fibers, sheets, films, sheets, strands, flakes, rods, nuggets, discs, cubes, granules, agglomerates, or extrudates.

107. The process of any one of claims 101 to 106, wherein the intermediate composite structure is further processed to reduce the size of the particles and yield a comminuted composite structure.

108. The process of claim 107, wherein the comminuted composite is the lithium-selective ion exchange material composition.219326623476v2Attorney Docket No.: 733PCT601109. The process of claim 107, wherein the comminuted composite structure is sized to yield the lithium-selective ion exchange material composition.

110. The process of claims 107 or 109, wherein the size of the particles of is reduced by a method selected from: crushing, grinding, cutting, attrition, milling (including jet milling, cryo milling, ball milling, hammer milling, pin milling, disc milling, roller milling, attrition milling, fluid energy milling, ultrasonic milling, high-shear milling, wet milling, dry milling, bead milling, vibratory milling, planetary ball milling, fluid bed milling, pancake milling, loop milling, ball milling, impact milling, colloid milling, air-jet milling, conical milling), delumping, granulating, self-attrition, shredding, pulverization, micronization, ultrasonic treatment, or other methods of size reduction acting through the forces of impact, shear, compression, combinations, or process integrations thereof.

111. The process of any one of claims 60 to 110, wherein the one or more matrix materials comprises TiO2, ZrO2, SiO2, Al2O3, solid solutions thereof, or mixed oxides thereof, or combinations thereof.

112. The process of any one of claims 60 to 110, wherein the one or more matrix materials comprise one or more of: polyvinylidene fluoride, polyvinyl fluoride, polyvinyl chloride, polyvinylidene chloride, a chloro-polymer, a fluoro-polymer, a fluoro-chloro-polymer, polyethylene, polypropylene, polyphenylene sulfide, polytetrafluoroethylene, sulfonated polytetrafluoroethylene, polystyrene, polydivinylbenzene, polybutadiene, a sulfonated polymer, a carboxylated polymer, polyacrylonitrile, perfluoro-3,6-dioxa-4-methyl-7-octene- sulfonic acid, copolymers thereof, or combinations thereof.dioxa-4-methyl-7-octene-sulfonic acid, copolymers thereof, or combinations thereof.

113. The process of any one of claims 60 to 112, wherein the mass ratio of the one or more matrix materials to mixed metal oxide is from about 50:1 to about 1:50.

114. The process of any one of claims 60 to 112, wherein the mass ratio of the one or more matrix materials to mixed metal oxide is from about 1:1 to about 1:20.

115. The process of any one of claims 60 to 112, wherein the mass ratio of the one or more matrix materials to mixed metal oxide is from about 1:1 to about 1:5.

116. The process of any one of claims 60 to 115, wherein:a) the first matrix material is selected from: comprises T1O2. ZrO2. S1O2. AI2O3. solid solutions thereof, or mixed oxides thereof, or combinations thereof;b) the second matrix material is selected from: polyvinylidene fluoride, polyvinyl fluoride, polyvinyl chloride, polyvinylidene chloride, a chloro-polymer, a fluoro-polymer, a fluoro- 220326623476v2Attorney Docket No.: 733PCT601chloro-polymer, polyethylene, polypropylene, polyphenylene sulfide, polytetrafluoroethylene, sulfonated polytetrafluoroethylene, polystyrene, polydivinylbenzene, polybutadiene, a sulfonated polymer, a carboxylated polymer, polyacrylonitrile, perfluoro-3,6-dioxa-4-methyl-7-octene-sulfonic acid (Nafion®), copolymers thereof, or combinations thereof. dioxa-4-methyl-7-octene-sulfonic acid, copolymers thereof, or combinations thereof.

117. The process of any one of claims 60 to 115, wherein:a) the first matrix material is selected from: polyvinylidene fluoride, polyvinyl fluoride, polyvinyl chloride, polyvinylidene chloride, a chloro-polymer, a fluoro-polymer, a fluorochloro-polymer, polyethylene, polypropylene, polyphenylene sulfide, polytetrafluoroethylene, sulfonated polytetrafluoroethylene, polystyrene, polydivinylbenzene, polybutadiene, a sulfonated polymer, a carboxylated polymer, polyacrylonitrile, perfluoro-3,6-dioxa-4-methyl-7-octene-sulfonic acid (Nafion®), copolymers thereof, or combinations thereof.dioxa-4-methyl-7-octene-sulfonic acid, copolymers thereof, or combinations thereof;b) the second matrix material is selected from: comprises TiO2, ZrO2, SiO2, Al2O3, solid solutions thereof, or mixed oxides thereof, or combinations thereof.

118. The process of any one of claims 60 to 117, wherein at least two, at least three, at least four, or at least five matrix materials are used to coat, embed, adhere, or otherwise support the mixed metal oxides to form the lithium-selective ion exchange material composition.

119. The process of any one of claims 60 to 118, wherein particles of a mixed metal oxide are mixed with the intermediate composite structure, comminuted composite stmcture, or any classified particles therefrom.

120. The process of any one of claims 60 to 119, wherein the particles of said mixed metal oxide comprise undersized particles that were rejected during the controlling of the size of the mixed metal oxide.

121. The process of any one of claims 60 to 120, wherein the ratio of mixed metal oxide to composite stmcture or comminuted composite stmcture is from 50:1 to about 1:50 on a mass basis.

122. The process of any one of claims 60 to 121, wherein said mixture is controlled by processing the mixture through a classification unit.

123. The process of any one of claims 60 to 122, wherein the pore volume of the lithiumselective ion exchange material composition is at least about 0.001 mL / g, at least about 0.005221326623476v2Attorney Docket No.: 733PCT601mL / g, at least about 0.01 mL / g, at least about 0.05 mL / g, at least about 0.1 mL / g, at least about 0.2 mL / g, or at least about 0.3 mL / g.

124. The process of any one of claims 60 to 122, wherein the pore volume of the lithiumselective ion exchange material composition is from about 0.01 to 0.3 mL / g.

125. The process of any one of claims 60 to 122, wherein the pore volume of the lithiumselective ion exchange material composition is from about 0.05 to 0.2 mL / g.

126. The process of any one of claims 60 to 125, wherein the specific surface area of the lithium-selective ion exchange material composition is at least about 1 m2 / g, at least about 5 m2 / g, at least about 10 m2 / g, at least about 25 m2 / g, at least about 50 m2 / g, or at least about 100 m2 / g.

127. The process of any one of claims 60 to 125, wherein the specific surface area of the lithium-selective ion exchange material composition is from about 1 to 100 m2 / g.

128. The process of any one of claims 60 to 125, wherein the specific surface area of the lithium-selective ion exchange material composition is from about 20 to 70 m2 / g.

129. The process of any one of claims 60 to 128, wherein the characteristic diameter of 95 wt% of the of the particles lithium-selective ion exchange material composition is from about 100 to 200 µm, about 150 to 200 µm, about 200 to 300 µm, about 250 to 300, µm, about 100 to 200 µm, about 5 to 100 µm, about 25 to 100 µm, about 45 to 100 µm, about 60 to 100 µm, about 5 to 150 µm, about 10 to 150 µm, about 25 to 150 µm, about 45 to 150 µm, or about 60 to 150 µm.. The process of any one of claims 60 to 128, wherein the characteristic diameter of 90 wt% of the particles of the lithium-selective ion exchange material composition is from about 100 to 200 µm, about 150 to 200 µm, about 200 to 300 µm, about 250 to 300, µm, about 100 to 200 µm, about 5 to 100 µm, about 25 to 100 µm, about 45 to 100 µm, about 60 to 100 µm, about 5 to 150 µm, about 10 to 150 µm, about 25 to 150 µm, about 45 to 150 µm, or about 60 to 150 µm.. The process of any one of claims 60 to 128, wherein the d3of the particles of the lithium-selective ion exchange material composition is about 5 µm, about 10 pm, about 25 pm, about 50 pm, about 60 pm, about 75 pm, or about 100 pm.

132. The process of any one of claims 60 to 128, wherein the d5of the particles of the lithium-selective ion exchange material composition is about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 60 µm, about 75 µm, or about 100 µm.326623476v2Attorney Docket No.: 733PCT601133. The process of any one of claims 60 to 128, wherein the dio of the particles of the lithium-selective ion exchange material composition is about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 60 µm, about 75 µm, or about 100 µm.. The process of any one of claims 60 to 128, wherein the d90of the particles of the lithium-selective ion exchange material composition is about 75 µm, about 100 µm, about 150 µm, about 200 µm, or about 300 µm.. The process of any one of claims 60 to 128, wherein the d95of the particles of the lithium-selective ion exchange material composition is about 75 µm, about 100 µm, about 150 µm, about 200 µm, or about 300 µm.

136. The process of any one of claims 60 to 128, wherein the d97of the particles of the lithium-selective ion exchange material composition is about 75 µm, about 100 µm, about 150 µm, about 200 µm, or about 300 µm.

137. The process of any one of claims 60 to 136, wherein the composition exhibits a lithium leach percent of at least about 60%, at least about 70%, at least about 75%, at least about 85%, at least about 90%, at least about 95%, or at least about 99%.

138. The process of any one of claims 60 to 136, wherein the composition exhibits a lithium extraction percent of at least about 50%, at least about 60%, at least about 70%, at least about 75%, at least about 85%, at least about 90%, at least about 95%, or at least about 99%.

139. The process of any one of claims 60 to 138, wherein the source of lithium is a low grade brine with a lithium concentration of under 2,500 mg / L of lithium.

140. The process of any one of claims 60 to 138, wherein the lithium concentration of under 1,000 mg / L of lithium.

141. The process of any one of claims 60 to 138, wherein the lithium concentration of under 100 mg / L of lithium.

142. The process of any one of claims 60 to 141, wherein the settling velocity the lithiumselective ion exchange material composition in water at room temperature is at least 0.1 cm / min, at least 1 cm / min, at least 5 cm / min, at least 10 cm / min, at least 50 cm / min, at least 100 cm / min, at least 1,000 cm / min or at least 1,500 cm / min.

143. The process of any one of claims 60 to 141, wherein the settling velocity the lithiumselective ion exchange material composition in water at room temperature is from 0.1 to 1,500 cm / min.223326623476v2Attorney Docket No.: 733PCT601144. The process of any one of claims 60 to 141, wherein the settling velocity the lithiumselective ion exchange material composition in water at room temperature is from 30 to 100 cm I min.

145. The process of claim any one of claims 60 to 144 wherein the lithium-selective ion exchange material composition has the following hydrodynamic characteristics:i) the pressure drop of water flowing through a packed bed of said composition at most 50 psi / cm as water flows though the bed at a superficial velocity of 5 cm / min; and ii) the settling velocity of said particles in water at room temperature at least 0.1 cm / min.

146. The process of any one of claims 60 to 145, wherein a packed bed said composition exhibit a pressure drop of at most 1 psi / cm, 3 psi / cm, 5 psi / cm, 10 psi / cm, 20 psi / cm, 40 psi / cm, 80 psi / cm, or 100 psi / cm, as water flows through the bed at a superficial velocity of 0.5 cm / min.

147. The process of any one of claims 60 to 145, wherein a packed bed said composition exhibit a pressure drop of at most 1 psi / cm, 3 psi / cm, 5 psi / cm, 10 psi / cm, 20 psi / cm, 40 psi / cm, 80 psi / cm, or 100 psi / cm, as water flows through the bed at a superficial velocity of 1 cm / min.

148. The process of any one of claims 60 to 145, wherein a packed bed said composition exhibit a pressure drop of at most 1 psi / cm, 3 psi / cm, 5 psi / cm, 10 psi / cm, 20 psi / cm, 40 psi / cm, 80 psi / cm, or 100 psi / cm, as water flows through the bed at a superficial velocity of 5 cm / min.

149. The process of any one of claims 60 to 145, wherein a packed bed said composition exhibit a pressure drop of at most 1 psi / cm, 3 psi / cm, 5 psi / cm, 10 psi / cm, 20 psi / cm, 40 psi / cm, 80 psi / cm, or 100 psi / cm, as water flows through the bed at a superficial velocity of 10 cm / min.

150. The process of any one of claims 60 to 149, wherein the mixed metal oxide is generated from a metal precursor and a lithium salt precursor.

151. The process of claim 150, wherein the lithium salt precursor is selected from: lithium sulfate, lithium carbonate, lithium nitrate, lithium phosphate, lithium hydroxide, lithium chloride, hydrates thereof, or combinations thereof.

152. The process of claims 150 or 151, wherein the metal precursor is selected from:titanium dioxide, titanium alkoxides, titanium chloride, manganese dioxide, manganese oxide, manganese carbonate, manganese acetate, manganese hydroxide, manganese nitrate,224326623476v2Attorney Docket No.: 733PCT601manganese sulfate, manganese phosphate, NixMnyCo1-x-y(OH)2, NixMnyAl1-x-y(OH)2, solid solutions thereof, or combinations thereof.

153. The process of any one of claims 150 to 152, wherein the metal precursor has a d5particle size of about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm, or about 1 mm.

154. The process of any one of claims 1 tol50 to 152, wherein the metal precursor has a d10particle size of about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm, or about 1 mm.. The process of any one of claims 1 to 150 to 152, wherein the metal precursor has a d90particle size of about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm, or about 1 mm.

156. The process of any one of claims 1 to 150 to 152, wherein the metal precursor has a d95particle size of about 0.1 µm, about 0.5 µm, about 1 µm, about 5 µm, about 10 µm, about 25 µm, about 50 µm, about 75 µm, about 100 µm, about 250 µm, about 500 µm, or about 1 mm.

157. The lithium-selective ion exchange material composition manufactured by the process of any one of claims 60 to 156.

158. A method of extracting lithium from a liquid resource through the reversible exchange of hydrogen and lithium, the method comprising:i) treating the lithium-selective ion exchange material composition of any one of claims 1 to 59 with an acid to release lithium and yield a protonated lithium-selective ion exchange material,ii) performing lithium extraction cycles, wherein each cycle comprises(1) contacting the protonated lithium-selective ion exchange material to a liquid resource to absorb lithium therefrom and yield a lithium-enriched lithiumselective ion exchange material;(2) treating the lithium-enriched lithium-selective ion exchange material with an acid eluent solution to yield a synthetic lithium solution and regenerate the protonated lithium-selective ion exchange material.

159. The method of claim 158, wherein the acid comprises hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, chloric acid, perchloric acid, nitric acid, formic acid, carbonic acid, acetic acid, or combinations thereof.

160. The method of claims 158 or 159, wherein the concentration of the acid is selected from a range of: 0.1 - 0.5, 0.5 - 1, 1 - 2, 2 - 5, or 5 - 10 mol of H+equivalents per liter.225326623476v2Attorney Docket No.: 733PCT601161. The method of claims 158 or 159, wherein [N - 3](i) comprises treating the lithiumselective ion exchange material composition with a molar ratio of H+equivalents to lithium in the range of: 0.1 - 0.5, 0.5 - 0.75, 0.75 - 1.0, 1.0 - 1.25, 1.25 - 1.5, 1.5 - 2, 2 - 3, 3 - 5, or 5 - 10.

162. The method of any one of claims 158 to 161, wherein said liquid resource is selected the following list: a natural brine, a saline lake brine, a dissolved salt flat brine, a geothermal brine, seawater, concentrated seawater, desalination effluent, a concentrated brine, a processed brine, liquid from an ion exchange process, liquid from a solvent extraction process, a synthetic brine, leachate from ores, leachate from minerals, leachate from clays, leachate from sediments, leachate from recycled products, leachate from recycled materials, or combinations thereof.

163. The method of any one of claims 158 to 162, wherein the concentration of lithium in the liquid resource is greater than 1, 5, 10, 50, 100, 500, 1000, or 2000 mg / L.

164. The method of any one of claims 158 to 163, wherein treating the lithium-enriched lithium-selective protonated ion exchange material with an acidic eluent solution yields a synthetic lithium solution and regenerates the protonated lithium-selective ion exchange material, andwherein said acid comprises hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, chloric acid, perchloric acid, nitric acid, formic acid, carbonic acid, acetic acid, or combinations thereof.

165. The method of claim 164, wherein the acid concentration in the eluent solution is from 0.01 M and 0.1 M, 0.1 M and 1 M, 1 M and 2 M, 2 M and 3 M, or 3 M and 5 M.

166. The method of any one of claims 158 to 165, further comprising contacting a chemical additive to the lithium-enriched lithium-selective protonated ion exchange material or lithium-selective ion exchange material composition.

167. The method of claim 166, wherein said chemical additive comprises oxygen, air, ozone, hydrogen peroxide, fluorine, chlorine, bromine, iodine, a nitrate compound, sodium hypochlorite, sodium persulfate, bleach, a chlorite, a chlorate, a perchlorate, potassium permanganate, a permanganate, sodium perborate, a perborate, mixtures thereof or combinations thereof.

168. The method of claims 166 or 167, wherein contacting the ion exchange material to the chemical additive reduces the dissolution of the lithium-selective ion exchange material composition into the acid or liquid resource.226326623476v2Attorney Docket No.: 733PCT601169. The method of any one of claims 158 to 168, wherein [N - 1] (ii) is repeated greater than about 100, 500, 1,000, 2,000, 3,000, 5,000, 7,000, or 10,000 times to extract lithium.

170. The process of any one of claims 158 to 169, wherein the lithium extraction percent in step ii) of at least about 50%, at least about 60%, at least about 70%, at least about 75%, at least about 85%, at least about 90%, at least about 95%, or at least about 99%.

171. The method of any one of claims 158 to 170, wherein the extraction of lithium would be lower if the metal precursor, mixed metal oxide, or comminuted composite structure, or the lithium-selective ion exchange material composition were not sized.

172. The method of any one of claims 158 to 170, wherein the purity of the synthetic lithium solution would be lower if the metal precursor, mixed metal oxide, or comminuted composite structure, or the lithium-selective ion exchange material composition were not sized.

173. The method of any one of claims 158 to 170, wherein the dissolution of the lithiumselective ion exchange material composition would be higher if the metal precursor, mixed metal oxide, or comminuted composite structure were not sized.

174. The method of any one of claims 158 to 173, wherein the protonated lithium-selective ion exchange material or lithium-enriched lithium-selective ion exchange material is treated to regenerate a recycled lithium-selective ion exchange material.

175. The method of any one of claims 158 to 174, wherein the molar ratio of lithium to transition metal in the protonated lithium-selective ion exchange material is from 0.01:1 to 3:1.

176. The method of any one of claims 158 to 175, wherein the molar ratio of lithium to transition metal in the lithium-enriched lithium-selective ion exchange material is from 0.1:1 to 4:1.

177. The method of any one of claims 158 to 176, wherein the protonated lithium-selective ion exchange material or lithium-enriched lithium-selective ion exchange material is treated with a lithium salt precursor to regenerate the recycled lithium-selective ion exchange material.

178. The method of claim 177, wherein the lithium salt precursor is selected from: lithium sulfate, lithium carbonate, lithium nitrate, lithium phosphate, lithium hydroxide, lithium chloride, or combinations thereof.

179. The method of claim 177 or 178, wherein the regeneration comprises a heat treatment.227326623476v2Attorney Docket No.: 733PCT601180. The method of claim 179, wherein said heat treatment occurs in a pusher kiln, a roller hearth kiln, a rotary kiln, a rotary furnace, a muffle furnace, a batch furnace, or a continuous furnace.

181. The method of claims 179 or 180, wherein the heat treatment occurs at a temperature of 270 K to about 280 K, from about 280 K to about 290 K, from about 290 K to about 300 K, from about 300 K to about 310 K, from about 310 K to about 320 K, from about 320 K to about 330 K, from about 330 K to about 340 K, from about 340 K to about 350 K, from about 350 K to about 360 K, from about 360 K to about 370 K, from about 370 K to about 380 K, from about 380 K to about 390 K, from about 390 K to about 400 K, from about 400 K to about 410 K, from about 410 K to about 420 K, from about 420 K to about 430 K, from about 430 K to about 440 K, from about 440 K to about 450 K, from about 450 K to about 460 K, from about 460 K to about 470 K, 470 K to about 480 K, from about 480 K to about 490 K, from about 490 K to about 500 K, from about 500 K to about 510 K, from about 510 K to about 520 K, from about 520 K to about 530 K, from about 530 K to about 540 K, from about 540 K to about 550 K, from about 550 K to about 560 K, from about 560 K to about 570 K, from about 570 K to about 580 K, from about 580 K to about 590 K, from about 590 K to about 600 K, from about 600 K to about 610 K, from about 610 K to about 620 K, from about 620 K to about 630 K, from about 630 K to about 640 K, from about 640 K to about 650 K, from about 650 K to about 660 K, from about 660 K to about 670 K, from about 670 K to about 680 K, from about 680 K to about 690 K, from about 690 K to about 700 K, from about 700 K to about 710 K, from about 710 K to about 720 K, from about 720 K to about 730 K, from about 730 K to about 740 K, from about 740 K to about 750 K, from about 750 K to about 760 K, from about 760 K to about 770 K, from about 770 K to about 780 K, from about 780 K to about 790 K, from about 790 K to about 800 K, from about 800 K to about 810 K, from about 810 K to about 820 K, from about 820 K to about 830 K, from about 830 K to about 840 K, from about 840 K to about 850 K, from about 850 K to about 860 K, from about 860 K to about 870 K, from about 870 K to about 880 K, from about 880 K to about 890 K, from about 890 K to about 900 K.

182. The method of any one of claims 177 to 181, wherein the protonated lithium-selective ion exchange material or lithium-enriched lithium-selective ion exchange material comprises one or more matrix materials, and said one or more matrix materials are removed before treatment with the lithium salt precursor.228326623476v2Attorney Docket No.: 733PCT601183. The method of claim 182, wherein removal comprises heating to melt, combust, or degrade the matrix material.

184. The method of claim 182, wherein removal comprises dissolving the matrix material in a solvent.

185. The method of claim 182, wherein removal comprises dissolving the lithium-selective ion exchange material in an acid, to generate a solution of lithium and a transition metal, and further generating a lithium salt precursor and a metal precursor from the solution of lithium and a transition metal.

186. The method of any one of claims 174 to 185, wherein the recycled lithium-selective ion exchange material exhibits greater than 75 %, greater than 80 %, greater than 85 %, greater than 90 %, greater than 95 %, or greater than 99 % of the lithium ion exchange capacity as the lithium-selective ion exchange material.

187. The method of any one of claims 174 to 186, wherein the protonated lithium-selective ion exchange material or lithium-enriched lithium-selective ion exchange material is treated to regenerate a recycled lithium-selective ion exchange material after about 100, 300, 500, 1,000, 2,000, 4,000, 7,000, or 10,000 cycles of ion exchange.

188. The method of any one of claims 174 to 187, wherein the recycled lithium-selective ion exchange material extracts lithium from a liquid resource through the reversible exchange of hydrogen and lithium, in a process comprising:i) First, treating the recycled lithium-selective ion exchange material with an acid to release lithium and yield a protonated recycled lithium-selective ion exchange material,ii) Second, performing lithium extraction cycles, wherein each cycle comprises(1) contacting the protonated recycled lithium-selective ion exchange material to a liquid resource to absorb lithium therefrom and yield a lithium-enriched recycled lithium-selective ion exchange material;(2) treating the lithium-enriched recycled lithium-selective ion exchange material with an acid eluent solution to yield a synthetic lithium solution and regenerate the protonated recycled lithium-selective ion exchange material.

189. A method of extracting lithium from a liquid resource with recycled lithium-selective ion exchange material, the method comprising:229326623476v2Attorney Docket No.: 733PCT601i) treating the recycled lithium-selective ion exchange material composition of any one of claims 1 to 59 with an acid to release lithium and yield a recycled protonated lithium-selective ion exchange material,ii) performing lithium extraction cycles, wherein each cycle comprises(1) contacting the recycled protonated lithium-selective ion exchange material to a liquid resource to absorb lithium therefrom and yield a recycled lithium-enriched lithium-selective ion exchange material;(2) treating the recycled lithium-enriched lithium-selective ion exchange material with an acid eluent solution to yield a synthetic lithium solution and regenerate the recycled protonated lithium-selective ion exchange material.

190. The method of any one of claims 1 to 189, wherein the recycling process is performed at least 2, 3, 4, 5, 6, 7, 8, 9, or 10 times.

191. A lithium-selective ion exchange material composition, the composition comprising: a mixed metal oxide,wherein the mixed metal oxide comprises lithium, oxygen, and a transition metal, wherein the transition metal is selected from titanium and manganese, and wherein the molar ratio of lithium to transition metal is from about 0.25: 1 to about 4:1; anda first amount of first fines that are bonded to the mixed metal oxide,wherein the composition is in the form of particles,wherein the particles have (i) a d10particle size of greater than about 1 µm, and (ii) a d90particle size of less than about 1 mm, andwherein the first amount of the first fines comprises less than about 10 volume percent of the composition.

192. The composition of claim 191, wherein the particles have a specific pore volume of about 0.01 ml / g to about 0.25 ml / g, as determined by N2 physisorption, and a specific surface area of about 1 m2 / g to about 100 m2 / g, as determined by the Brunauer-Emmett-Teller (BET) method using N2 physisorption data.

193. The composition of claim 191 or 192, wherein the first amount of the first fines comprises less than about 5 volume percent of the composition.

194. The composition of claim 191 or 192, wherein the first amount of the first fines comprises less than about 4 volume percent of the composition.230326623476v2Attorney Docket No.: 733PCT601195. The composition of claim 191 or 192, wherein the first amount of the first fines comprises less than about 3 volume percent of the composition.

196. The composition of claim 191 or 192, wherein the first amount of the first fines comprises less than about 2 volume percent of the composition.

197. The composition of claim 191 or 192, wherein the first amount of the first fines comprises less than about 1 volume percent of the composition.

198. The composition of any of claims 191 to 197, wherein the first fines have an average diameter of less than about 10 pm.

199. The composition of any of claims 191 to 197, wherein the first fines have an average diameter of less than about 25 μm.

200. The composition of any of claims 191 to 197, wherein the first fines have an average diameter of less than about 40 pm.

201. The composition of any of claims 191 to 200, wherein the mixed metal oxide is a lithium-selective ion exchange material comprising LiMnPO4, Li2TiO3, Li2Ti2O5, Li2MnO3, Li2Mn2O5, Li4Ti5O12, Li4Mn5O12, LiTi2O4, LiMn2O4, Li1.6Mn1.6O4, solid solutions thereof, or combinations thereof.

202. The composition of any of claims 191 to 201, wherein a pore volume of the lithiumselective ion exchange material composition is from about 0.005 mL / g to about 0.3 mL / g.

203. The composition of any of claims 191 to 202, wherein a characteristic diameter of 90 wt% of the particles of the lithium-selective ion exchange material composition is from about 30 pm to about 200 pm.

204. The composition of any of claims 191 to 203, wherein the particles of the lithiumselective ion exchange material composition have (i) a d3particle size of about 20 μm, (ii) a d5particle size of about 30 μm, (iii) a d10particle size of about 40 μm, (iv) a d90particle size of about 140 μm, (v) a d95particle size of about 155 μm, (vi) a d97particle size of about 175 μm, or (vii) a combination thereof.

205. The composition of any of claims 191 to 204, wherein:the mixed metal oxide is generated from a metal precursor and a lithium salt precursor, the lithium salt precursor comprises lithium sulfate, lithium carbonate, lithium nitrate, lithium phosphate, lithium hydroxide, lithium chloride, hydrates thereof, or combinations thereof, and231326623476v2Attorney Docket No.: 733PCT601the metal precursor comprises titanium dioxide, titanium alkoxides, titanium chloride, manganese dioxide, manganese oxide, manganese carbonate, manganese acetate, manganese hydroxide, manganese nitrate, manganese sulfate, manganese phosphate, solid solutions thereof, or combinations thereof.

206. The composition of claim 205, wherein the metal precursor has (i) a d5particle size of about 20 μm, (ii) a d10particle size of about 30 μm, (iii) a d90particle size of about 120 μm, (iv) a d95particle size of about 140 μm, or (v) a combination thereof.

207. A method for manufacturing the lithium-selective ion exchange material composition of any of claims 191 to 206, the method comprising:contacting a lithium salt precursor with a metal precursor to generate a synthesis mixture;heating the synthesis mixture to form an intermediate mixed metal oxide, wherein the intermediate mixed metal oxide comprises a second amount of the first fines that are bonded to the intermediate mixed metal oxide, the second amount being greater than the first amount; andremoving a first portion of the second amount of the first fines from the intermediate mixed metal oxide to thereby generate the lithium-selective ion exchange material composition of any of claims 191 to 206.

208. The method of claim 207, wherein removing the first portion of the second amount of the first fines from the intermediate mixed metal oxide comprises:detaching a second portion of the second amount of the first fines from the intermediate mixed metal oxide using mechanical attrition; andseparating a first portion of the detached second portion from the intermediate mixed metal oxide.

209. The method of claim 208, wherein the mechanical attrition comprises one or more of sonication, high-shear mixing, low-speed mixing, tumbling, vibration, or a combination thereof.

210. The method of claim 208 or 209, wherein separating the first portion of the detached second portion from the intermediate mixed metal oxide is performed using one or more of wet sieving, hydrocyclone separations, classification, clarification, filtration, or a combination thereof.

211. The method of any of claims 207 to 210, further comprising: selectively sizing one or more of the intermediate mixed metal oxide, the mixed metal oxide, the metal precursor, the 232326623476v2Attorney Docket No.: 733PCT601lithium salt precursor, the lithium-selective ion exchange material composition, or any combination thereof.

212. A method of extracting lithium from a liquid resource, the method comprising:performing at least 100 lithium extraction cycles using the lithium-selective ion exchange material composition of any of claims 191 to 206 without releasing more than a second amount of the first fines from the mixed metal oxide,wherein the second amount comprises about 5 weight percent of the composition, andwherein the first fines having a diameter of less than about 25 pm.

213. The method of claim 212, wherein the second amount comprises about 4 weight percent of the composition.

214. The method of claim 212, wherein the second amount comprises about 3 weight percent of the composition.

215. The method of claim 212, wherein the second amount comprises about 2 weight percent of the composition.

216. The method of claim 212, wherein the second amount comprises about 1 weight percent of the composition.

217. A method for manufacturing a lithium-selective ion exchange material composition, the method comprising:contacting a lithium salt precursor with a metal precursor to generate a synthesis mixture;heating the synthesis mixture to form an intermediate mixed metal oxide, wherein the intermediate mixed metal oxide comprises a first amount of first fines that are bonded to the intermediate mixed metal oxide; and removing a first portion of the first amount of the first fines from the intermediate mixed metal oxide to thereby generate a lithium-selective ion exchange material composition,wherein the composition is in the form of particles and comprises less than about 10 volume percent of the first fines, andwherein about 90 weight percent of the composition has a particle size from about 10 pm to about 300 pm.

218. The method of claim 217, wherein removing the first portion of the first amount of the first fines from the intermediate mixed metal oxide comprises:233326623476v2Attorney Docket No.: 733PCT601detaching a second portion of the first amount of the first fines from the intermediate mixed metal oxide using mechanical attrition; andseparating a first portion of the detached second portion from the intermediate mixed metal oxide.

219. The method of claim 218, wherein the mechanical attrition comprises one or more of sonication, high-shear mixing, low-speed mixing, tumbling, vibration, or a combination thereof.

220. The method of claim 218 or 219, wherein separating the first portion of the detached second portion from the intermediate mixed metal oxide is performed using one or more of wet sieving, hydrocyclone separations, classification, clarification, filtration, or a combination thereof.

221. The method of claim 220, wherein the wet sieving is performed using a mesh comprising one or more opening sizes, and wherein the one or more opening sizes comprise about 63 pm, about 53 pm, about 44 pm, about 37 pm, about 25 pm, about 20 pm, or combinations thereof.

222. The method of any of claims 217 to 221, further comprising:selectively sizing one or more of the intermediate mixed metal oxide, the mixed metal oxide, the metal precursor, the lithium salt precursor, the lithium-selective ion exchange material composition, or any combination thereof.

223. The method of claim 222, wherein selectively sizing is performed using one or more of dry sieving, classification, air classification, wet sieving, or a combination thereof.

224. The method of any of claims 217 to 223, wherein:before removing the first portion of the first amount of the first fines from the intermediate mixed metal oxide, the intermediate mixed metal oxide comprises at least about 5 volume percent of the first fines, andafter removing the first portion of the first amount of the first fines from the intermediate mixed metal oxide, the intermediate mixed metal oxide comprises less than about 4 volume percent of the first fines.

225. The method of any of claims 218 to 224, wherein the mechanical attrition comprises sonication that is performed at an energy density of about 8 to about 29,000 watt-hour per kilogram (Wh / kg) of the intermediate mixed metal oxide.

226. The method of any of claims 217 to 225, wherein the intermediate mixed metal oxide comprises about 30 to about 95 volume percent less of the first fines after removing the first234326623476v2Attorney Docket No.: 733PCT601portion of the first amount of the first fines as compared to before removing the first portion of the first amount of the first fines.

227. The method of any of claims 217 to 223 or 225 to 226, wherein:before removing the first portion of the first amount of the first fines from the intermediate mixed metal oxide, the intermediate mixed metal oxide comprises at least about 4 volume percent of the first fines, andafter removing the first portion of the first amount of the first fines from the intermediate mixed metal oxide, the intermediate mixed metal oxide comprises less than about 2 volume percent of the first fines.

228. The method of any of claims 217 to 227, wherein the mixed metal oxide, the lithium salt precursor, the metal precursor, or the lithium-selective ion exchange material composition is sized to have (i) a d5particle size of about 30 μm, (ii) a d10particle size of about 40 μm, (iii) a d90particle size of about 140 μm, (iv) a d95particle size of about 155 μm, or (v) a combination thereof.

229. A method of extracting lithium from a liquid resource, the method comprising:performing at least 100 lithium extraction cycles using a lithium-selective ion exchange material composition,wherein the composition comprises a mixed metal oxide,wherein prior to performing the at least 100 lithium extraction cycles, the composition comprises a first amount of first fines that are bonded to the mixed metal oxide, andwherein performing the at least 100 lithium extraction cycles releases no more than a second amount of first fines from the mixed metal oxide, the second amount comprising about 5 weight percent of the composition.

230. The method of claim 229, wherein the first fines have a diameter of less than about 10 pm.

231. The method of claim 229, wherein the first fines have a diameter of less than about 25 pm.

232. The method of claim 229, wherein the first fines have a diameter of less than about 40 pm.

233. The method of any of claims 229 to 232, wherein the first amount comprises less than about 10 volume percent of the composition.235326623476v2Attorney Docket No.: 733PCT601234. The method of any of claims 229 to 233, wherein the second amount comprises about 4 weight percent of the composition.

235. The method of any of claims 229 to 233, wherein the second amount comprises about 3 weight percent of the composition.

236. The method of any of claims 229 to 233, wherein the second amount comprises about 2 weight percent of the composition.

237. The method of any of claims 229 to 233, wherein the second amount comprises about 1 weight percent of the composition.236326623476v2

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