Lithium adsorbent compositions with enhanced intrinsic amorphicity

Abstract

The present disclosure relates to sorbents for selective metal extractions from solution, and more specifically to intrinsic-amorphicity enhanced high-hydration lithium incorporated aluminum hydroxide (IA-enhanced H 2 -LIAH) compositions configured for lithium extraction. The IA-enhanced H 2 -LIAH compositions of the present disclosure are differentiated from conventional LIAH compositions at least in part by their: (i) crystallization-hydrates : lithium molar ratios, (ii) amorphous aluminate content; and (iii) median crystallite size. As described herein, these features combine to provide desirable extraction-performance characteristics and desirable durability / robustness characteristics. The IA-enhanced H 2 -LIAH compositions of the present disclosure may be: (i) incorporated into sorbents for direct lithium extraction as described herein; (ii) synthesized by methods of manufacture as described herein; (iii) deployed in apparatus for recovering lithium from brine as set out herein; and / or (iv) deployed in methods for lithium recovery from brine as set out herein.

Description

LITHIUM ADSORBENT COMPOSITIONS WITH ENHANCED INTRINSIC AMORPHICITYCROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims priority under applicable laws to U.S. Provisional Patent Application No. US 63 / 718,225 filed on November 08, 2024, the content of which is incorporated herein by reference in its entirety for all purposes.TECHNICAL FIELD

[0002] The present disclosure relates generally to sorbents for selective metal extractions from solution, and more specifically to lithium-incorporated aluminumhydroxide (LIAH) compositions configured for lithium extraction.BACKGROUND

[0003] Lithium is a critical and technologically important element. It is used in ceramics, glass, lubricants, light-weight alloys, pharmaceuticals, and batteries. The use of lithium-ion batteries in portable electronic devices and electric vehicles has increased global demand for lithium.

[0004] Lithium is primarily found in three types of feedstocks: (i) pegmatites; (ii) hydrothermally altered clays; and (iii) continental brines. Continental brines have the potential to be the most economically and environmentally viable, but their lithium concentrations vary widely. By way of example, select brines from Salar de Atacama have an average lithium concentration of greater than 2,000 mg / L, whereas select brines from California’s Searles Lake have an average lithium concentration of about 65 mg / L. Continental brines also vary with respect to the spectrum and concentrations of other ions they contain. Sodium ions, potassium ions, magnesium ions, calcium ions, chloride ions, sulfate ions, and carbonate ions are ubiquitous in continental brines, and they can form a range of ionic salts. Taken together, the wide range of lithium concentrations and complex profiles of other ions present in continental brines introduce considerable challenges for lithium producers. These challenges are often compounded by remote and / or harshoperating conditions, complex regulatory requirements, restrictions on water use, and / or strict environmental standards.

[0005] Direct lithium extraction (DLE) processes are being developed to address these challenges. DLE processes typically employ sorbent technologies, ion-exchange technologies, and / or solvent exchange technologies to selectively extract lithium from brine. Sorbent technologies are particularly promising, and lithium-incorporated- aluminum-hydroxide (LIAH) compositions are a leading class of inorganic sorbents for DLE. LIAH compositions are commonly referred to as layered double hydroxide (LDH) sorbents in view of their common structural forms, and these names are used interchangeably in the present disclosure without limitation to any particular structural form.

[0006] Unfortunately, conventional methods for preparing LIAH compositions provide little opportunity to tailor the resultant materials towards desirable properties, such as high hardness, high selectivity for lithium, high lithium uptake capacity, narrow particle size distribution, etc. Gibbsite impregnation is a conventional approach to preparing conventional LIAH compositions. This process may be complicated by long preparation times, for example due to slow Gibbsite dissolution. Moreover, sorbents produced by Gibbsite impregnation tend to have low lithium uptake capacities.

[0007] In situ precipitation has been explored as a manufacturing process for conventional LIAH compositions. However, reported processes tend to yield products with broad particle size distributions, low crystallinity, and / or low lithium uptake capacities.

[0008] Hydrothermal processes have also been explored for the preparation of conventional LIAH compositions. Unfortunately, sorbents resultant of hydrothermal processes suffer from numerous limitations, and the processes themselves can introduce undesirable costs and / or complexities having regard to their high pressure and / or high temperature parameters.

[0009] There is an unmet need for novel LIAH compositions that are suitable for extracting lithium from brine. There is also an unmet need for: (i) methods of manufacturing that enable tailoring novel LIAH compositions to elicit both desirable extraction-performance characteristics and durability / robustness characteristics; (ii) apparatus for recovering lithium from brines that utilize novel LIAH compositions; and (iii) methods of recovering lithium from brine that utilize novel LIAH compositions.

[0010] In view of the forgoing, Applicant previously disclosed a novel class of LIAH compositions in International Publication WO 2023 / 212824A1 (and related applications) referred to as high-hydration lithium-incorporated-aluminum-hydroxide ( / 72-LIAH) compositions. The previously reported / 72-LIAH compositions feature a crystal lization-hydrate : lithium molar ratio of at least about 2.1 : 1.0. In this context, “crystallization-hydrate” generally refers to water that is incorporated within a crystal lattice - as opposed to surface-bound water - and it is detectable through routine analytical measures. As reported previously, the degree of crystallization-hydrate incorporation in / 72-LIAH compositions may be tailored through various synthetic protocols that utilize an unconventional pH effect to induce the formation of a gel-like material. In the context of the present disclosure, the previously reported / 72-LIAH compositions are referred to as first generation / 72-LIAH compositions.SUMMARY

[0011] Through extensive research and development, Applicant has again advanced the state of the art with respect to high-hydration lithium-incorporated-aluminum- hydroxide ( / 72-LIAH) compositions. As reported herein, the present inventors have developed protocols for manipulating key synthetic parameters during the formation and / or finishing of the gel-like material to enhance the intrinsic amorphicity of the resultant compositions. Those skilled in the art will appreciate that seeking enhanced intrinsic amorphicity is counterintuitive, as conventional wisdom prioritizes increased crystallinity {e.g., having regard to published mechanistic investigations, which show the importance of interactions between lithium cations and highly crystalline hydroxy-aluminates in sorbent compositions). In contrast, the present inventors posited that desirable extractionperformance characteristics may be elicited by enhancing intrinsic amorphicity to: (i) better support and / or position discrete crystalline active sites; and / or (ii) impact the size and / or morphology of the crystallites. The present inventors further posited that enhancing intrinsic amorphicity may also attenuate or eliminate or reduce the need for exogenousbinder by improving the intrinsic durability, shapeability, and / or ion-retention characteristics of the compositions they engender.

[0012] To these ends (inter alia), the present inventors developed a novel class of / 72-LIAH compositions - those having an amorphous aluminate content of at least about 20% and a median crystallite size of less than about 70 nm - that combine desirable extraction-performance characteristics and desirable durability / robustness characteristics to surprising degrees. These compositions are referred to herein as intrinsic-amorphicity- enhanced / 72-LIAH compositions (JA-enhanced / 72-LIAH compositions) to distinguish from the first generation / 72-LIAH compositions reported previously and the conventional LIAH compositions known in the art.

[0013] The lA-enhanced / 72-LIAH compositions of the present disclosure may be: (i) incorporated into sorbents for direct lithium extraction as described herein; (ii) synthesized by methods of manufacture as described herein; (iii) deployed in apparatus for recovering lithium from brine as set out herein; and / or (iv) deployed in methods for lithium recovery from brine as set out herein.

[0014] An aspect of the present disclosure relates to a sorbent for recovering lithium from a lithium containing solution, the sorbent comprising an lA-enhanced / 72-LIAH composition having: a crystallization-hydrate : lithium molar ratio of at least about 2.1 : 1.0; an amorphous aluminate content of at least about 20%; and a median crystallite size of less than about 70 nm.

[0015] In an embodiment of the present disclosure, the median crystallite size of the lA-enhanced / 72-LIAH composition is between about 0.5 nm and about 70 nm.

[0016] In an embodiment of the present disclosure, the median crystallite size of the lA-enhanced / 72-LIAH composition is between about 5 nm and about 20 nm.

[0017] In an embodiment of the present disclosure, the median crystallite size of the lA-enhanced / 72-LIAH composition is determined by scanning electron microscopy (SEM).

[0018] In an embodiment of the present disclosure, the amorphous content of the lA-enhanced / 72-LIAH composition is between about 20% and about 50%.

[0019] In an embodiment of the present disclosure, the amorphous content of the lA-enhanced / 72-LIAH composition is between about 23% and about 35%.

[0020] In an embodiment of the present disclosure, the amorphous content of the lA-enhanced / 72-LIAH composition is between about 26% and about 31%.

[0021] In an embodiment of the present disclosure, the amorphous content of the lA-enhanced / 72-LIAH composition is determined by X-ray diffraction (XRD).

[0022] In an embodiment of the present disclosure, the crystallization-hydrate : lithium molar ratio of the lA-enhanced / 72-LIAH composition is between about 2.1 : 1.0 and about 4.3 : 1.0.

[0023] In an embodiment of the present disclosure, the crystallization-hydrate : lithium molar ratio of the lA-enhanced / 72-LIAH composition is between about 2.4 : 1.0 and about 4.0 : 1.0.

[0024] In an embodiment of the present disclosure, the crystallization-hydrate : lithium molar ratio of the lA-enhanced / 72-LIAH composition is between about 2.7 : 1.0 and about 3.5 : 1.0.

[0025] In an embodiment of the present disclosure, the crystallization-hydrate : lithium molar ratio of the lA-enhanced / 72-LIAH composition is determined from differential scanning calorimetry (DSC), inductively-coupled plasma optical emission spectroscopy (ICP-OES), thermogravimetric analysis (TGA), or a combination thereof.

[0026] In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition has an X-ray diffraction (XRD) pattern having 20 reflectance peaks at approximately 11.5 °20, 20.1 °20, 23.1 °20, 35.0 °20, 35.7 °20, or a combination thereof.

[0027] In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition has an XRD pattern having an absence of 20 reflectance peaks at 18.2 °20.

[0028] In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition has an aluminum : lithium molar ratio of at least about 1.9 : 1.0.

[0029] In an embodiment of the present disclosure, the aluminum : lithium molar ratio of the lA-enhanced / 72-LIAH composition is between about 2.0 : 1.0 and about 3.5 : 1.0.

[0030] In an embodiment of the present disclosure, the aluminum : lithium molar ratio of the lA-enhanced / 72-LIAH composition is between about 2.4 : 1.0 and about 3.6 : 1.0.

[0031] In an embodiment of the present disclosure, the aluminum : lithium ratio of the lA-enhanced / 72-LIAH composition is determined from inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis.

[0032] In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition is as described in Formula 1:LiaX mAI(OH)3 nH2OCr Formula 1 wherein: a is about 1;X is a monovalent anion m is between about 1.9 and about 3.6; n is between about 2.1 and about 4.3; andFWcr specifies crystallization-hydrate

[0033] In an embodiment of the present disclosure, the monovalent anion X is chloride.

[0034] In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition is a lithium-aluminum-layered-double-hydroxide composition.

[0035] In an embodiment of the present disclosure, the sorbent further comprises a binding agent, an encapsulating agent, or a combination thereof.

[0036] In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition has a lithium-uptake capacity of at least about 8.0 mg / mL.

[0037] In an embodiment of the present disclosure, the lithium-uptake capacity of the lA-enhanced / 72-LIAH composition is at least about 9.0 mg / mL.

[0038] In an embodiment of the present disclosure, the lithium-uptake capacity of the lA-enhanced / 72-LIAH composition is between about 9.5 mg / mL and about 12.0 mg / mL.

[0039] In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition has a hardness value of at least about 30 psi.

[0040] In an embodiment of the present disclosure, the hardness value of the lA-enhanced / 72-LIAH composition is between about 32 psi and about 80 psi.

[0041] In an embodiment of the present disclosure, the hardness value of the lA-enhanced / 72-LIAH composition is determined by bulk crush strength analysis.

[0042] In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition has a slurry particle size distribution (PSD) d50 value of less than 90 pm.

[0043] In an embodiment of the present disclosure, the slurry PSD d50 value of the lA-enhanced / 72-LIAH composition is between about 10 pm and about 85 pm.

[0044] In an embodiment of the present disclosure, the slurry PSD d50 value of the lA-enhanced / 72-LIAH composition is between about 30 pm and about 50 pm.

[0045] In an embodiment of the present disclosure, the slurry PSD d50 value of the lA-enhanced / 72-LIAH composition is determined by laser diffraction particle size analysis.

[0046] In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition has a Brunauer-Emmett-Teller (BET) surface area of at least about 60 m2 / g.

[0047] In an embodiment of the present disclosure, the BET surface area of the lA-enhanced / 72-LIAH composition is between about 60 m2 / g and about 150 m2 / g.

[0048] In an embodiment of the present disclosure, the BET surface area of the lA-enhanced / 72-LIAH composition is between about 75 m2 / g and about 125 m2 / g.

[0049] In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition has a turbidity value of less than 60 NTU.

[0050] In an embodiment of the present disclosure, the turbidity value of the lA-enhanced / 72-LIAH composition is between about 5 NTU and about 55 NTU.

[0051] In an embodiment of the present disclosure, the turbidity of the lA-enhanced / 72-LIAH composition is determined with a turbidimeter by suspending the lA-enhanced / 72-LIAH composition in deionized water.

[0052] In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition is physically durable for at least about 2,000 column cycles.

[0053] An aspect of the present disclosure relates to a method of manufacturing an lA-enhanced / 72-LIAH composition, the method comprising:(i) contacting an initial aliquot of a hydroxide solution with a solution comprising a lithium halide and an aluminum halide to form a reaction mixture in which the lithium halide and aluminum halide are in excess such that the pH of the reaction mixture is reduced to less than about 2.0;(ii) adding an additional aliquot of the hydroxide solution to the reaction mixture to increase the pH of the reaction mixture to between about 1.5 and about 5.5;(iii) heating the reaction mixture to at least about 30 °C;(iv) aging the reaction mixture for about at least about 2 hours, after which time the mixture forms a gel-like material; and(v) adding an additional aliquot of the hydroxide solution to the reaction mixture to increase the pH of the reaction mixture to between about 5.5 and about 7.5.

[0054] In an embodiment of the present disclosure, in step (i) the solution comprising the lithium halide and the aluminum halide is added to the initial aliquot of the hydroxide solution.

[0055] In an embodiment of the present disclosure, in step (i) the hydroxide solution has a pH of between about 9.0 and about 13.5.

[0056] In an embodiment of the present disclosure, in step (i) the pH of the reaction mixture is reduced to between about 1.5 and about 4.0.

[0057] In an embodiment of the present disclosure, in step (ii) the reaction mixture is heated to at least about 35 °C.

[0058] In an embodiment of the present disclosure, in step (ii) the reaction mixture is heated to between about 35 °C and about 95 °C.

[0059] In an embodiment of the present disclosure, in step (iv) the gel-like material has a gel strength of at least about 125 Pa.

[0060] In an embodiment of the present disclosure, in step (iv) the gel strength of the gel-like material is between about 125 Pa and about 400 Pa.

[0061] In an embodiment of the present disclosure, in step (iv) the gel strength of the gel-like material is between about 150 Pa and about 250 Pa.

[0062] In an embodiment of the present disclosure, in step (iv) the viscosity of the reaction mixture is between about 20,000 mPa*s and about 35,000 mPa*s.

[0063] In an embodiment of the present disclosure, in step (iv) the gel strength of the gel-like material is determined by rheometric analysis. The rheometric analysis was performed at about 3 RPM.

[0064] In an embodiment of the present disclosure, the initial aliquot of the hydroxide solution and the additional aliquots of the hydroxide solution are derived from the same stock solution.

[0065] In an embodiment of the present disclosure, the solution comprising the lithium halide and the aluminum halide has a lithium : aluminum molar ratio of between about 1.0 : 2.0 and about 1.0 : 3.0.

[0066] In an embodiment of the present disclosure, the hydroxide solution has a concentration of between about 15.0 w / w% and about 50.0 w / w%.

[0067] In an embodiment of the present disclosure, the lithium halide is lithium fluoride, lithium chloride, lithium bromide, lithium iodide, or a combination thereof.

[0068] In an embodiment of the present disclosure, the lithium halide is lithium chloride.

[0069] In an embodiment of the present disclosure, the aluminum halide is aluminum trifluoride, aluminum trichloride, aluminum tribromide, aluminum triiodide, or a combination thereof.

[0070] In an embodiment of the present disclosure, the aluminum halide is aluminum trichloride.

[0071] In an embodiment of the present disclosure, the hydroxide solution is a sodium hydroxide solution, a potassium hydroxide solution, a calcium hydroxide solution, a magnesium hydroxide solution, or a combination thereof.

[0072] In an embodiment of the present disclosure, the hydroxide solution is a sodium hydroxide solution.

[0073] In an embodiment of the present disclosure, in step (i), step (ii), step (iii), step (iv), step (v), or a combination thereof, the reaction mixture is agitated to modulate the viscosity of the reaction mixture.

[0074] In an embodiment of the present disclosure, in step (i), step (ii), step (iii), step (iv), step (v), or a combination thereof, the temperature of the reaction mixture is controlled to modulate the viscosity of the reaction mixture.

[0075] In an embodiment of the present disclosure, in step (i), step (ii), step (iii), step (iv), step (v), or a combination thereof, the pressure of the reaction mixture is controlled to modulate the viscosity of the reaction mixture.

[0076] In an embodiment of the present disclosure, in step (i), step (ii), step (iii), step (iv), step (v), or a combination thereof, the reaction time is controlled to modulate the viscosity of the reaction mixture.

[0077] In an embodiment of the present disclosure, the method further comprises: (vi) finishing the lA-enhanced / 72-LIAH composition by curing, aging, rinsing, desalting, drying, milling, and / or sieving the reaction mixture.

[0078] In an embodiment of the present disclosure, step (vi) comprises curing the reaction mixture for at least about 15 minutes.

[0079] In an embodiment of the present disclosure, in step (vi) the reaction mixture is cured for between about 15 minutes and about 20 hours.

[0080] In an embodiment of the present disclosure, step (vi) comprises desalting the reaction mixture by rinsing, washing, decanting, centrifuging, filtering, or a combination thereof.

[0081] In an embodiment of the present disclosure, step (vi) comprises desalting the reaction mixture by decanting.

[0082] In an embodiment of the present disclosure, step (vi) comprises drying the reaction mixture at or below about 760 mmHg.

[0083] In an embodiment of the present disclosure, step (vi) comprises drying the reaction mixture at a pressure between about 76 mmHg and 760 mmHg.

[0084] In an embodiment of the present disclosure, step (vi) comprises drying the reaction mixture at a temperature of at least about 70 °C.

[0085] In an embodiment of the present disclosure, step (vi) comprises drying the reaction mixture by indirect convective methods, direct convective methods, and / or conductive methods.

[0086] In an embodiment of the present disclosure, step (vi) comprises drying reaction mixture for between about 15 minutes and about 75 hours.

[0087] An aspect of the present disclosure relates to an apparatus for recovering lithium from a lithium containing solution, the apparatus comprising: a container having an inlet, an outlet, and a contiguous flow path therebetween; and a sorbent in the container, the sorbent comprising an lA-enhanced / 72-LIAH composition having: (i) a crystallization- hydrate : lithium molar ratio of at least about 2.1 : 1.0, (ii) an amorphous aluminate content of at least about 20%; and (iii) a median crystallite size of less than about 70 nm.

[0088] An aspect of the present disclosure relates to a method for recovering lithium from a lithium containing solution, the method comprising: contacting the lithium containing solution with a sorbent to extract lithium from the lithium containing solution; and eluting lithium from the sorbent to form a lithium-eluate solution, wherein the sorbent comprises an lA-enhanced / 72-LIAH composition having: (i) a crystal lization-hydrate : lithium molar ratio of at least about 2.1 : 1.0, (ii) an amorphous aluminate content of at least about 20%, and (iii) a median crystallite size of less than about 70 nm.BRIEF DESCRIPTION OF THE DRAWINGS

[0089] In the drawings and description provided herein, similar reference numerals indicate similar components. For sake of simplicity and clarity, not all drawings contain references to all the components and features, and references to some components and features may be found in only one drawing. Components and features of the present disclosure which are illustrated in other drawings can be readily inferred therefrom.

[0090] Figure 1 shows a differential scanning calorimetry (DSC) graph 100 depicting relative enthalpic variation as a function of temperature for a conventional lithium aluminum hydroxide (LIAH) composition and a high-hydration lithium-incorporatedaluminum-hydroxide ( / 72-LIAH) composition as described previously in Applicant’s international patent publication WO 2023 / 212824A1 (and related applications).

[0091] Figure 2 shows a normalized thermogravimetric analysis (TGA) plot 200 depicting sample weight changes (expressed as a relative percent) as a function of temperature as described previously in Applicant’s prior art publication WO 2023 / 212824A1 (and related applications). A series of / 72-LIAH compositions are shown, and their major decomposition events are indicated as described previously in Applicant’s international patent publication WO 2023 / 212824A1 (and related applications).

[0092] Figure 3 shows an overlay 300 of three X-ray diffraction (XRD) diffractograms. Two of the XRD diffractograms (311 and 321) are derived from / - / 2-LIAH compositions and the other (331) is derived from a conventional LIAH composition that was prepared by a Gibbsite impregnation method. The primary characteristic peaks of the / 72-LIAH compositions and the conventional LIAH composition are indicated as described previously in Applicant’s international patent publication WO 2023 / 212824A1 (and related applications).

[0093] Figure 4 shows a Fourier transform infrared (FTIR) spectra overlay 400 of an / 72-LIAH composition before 401 and after 402 high temperature drying. Primary aluminum-oxygen bonding absorbance bands are indicated as described previously in Applicant’s international patent publication WO 2023 / 212824A1 (and related applications).

[0094] Figure 5 shows an overlay 500 of XRD diffractograms depicting a characteristic crystalline pattern of a first generation / 72-LIAH composition 501 and that of an lA-enhanced / 72-LIAH composition of the present disclosure 502.

[0095] Figure 6 shows comparative scanning election microscope (SEM) images of a first generation / 72-LIAH composition (Panel 6A) and an lA-enhanced / 72-LIAH composition of the present disclosure (Panel 6B) with overlaid sizing measurements indicating crystallite size.

[0096] Figure 7 shows a curve 700 depicting lithium concentration as a function of time for an lA-enhanced / 72-LIAH composition across multiple lithium extraction cycles.

[0097] Figure 8 shows a schematic illustration 800 of an archetypal sorbent unit that comprises an array of columns for recovering lithium from a lithium containing solution in accordance with an embodiment of the present disclosure. Figure 8 also shows a method 850 in accordance with an embodiment of the present disclosure.DETAILED DESCRIPTION

[0098] The following detailed description and examples are illustrative and should not be interpreted as further limiting the scope of the invention. On the contrary, it is intended to cover all alternatives, modifications and equivalents that can be included as described by the present disclosure. Objects, advantages and other features of the compositions, methods and apparatus will be more apparent and better understood by those skilled in the art upon reading the following non-restrictive description and references made to the accompanying drawings.

[0099] The present disclosure relates to lithium-incorporated-aluminum-hydroxide (LIAH) compositions. The present disclosure differentiates high-hydration LIAH compositions ( / .e., / 72-LIAH compositions) from conventional LIAH compositions. In the context of the present disclosure, / 72-LIAH compositions have a crystallization-hydrate : lithium molar ratio of at least about 2.1 : 1.0, and conventional LIAH compositions do not. The present disclosure further differentiates between first generation / 72-LIAH compositions and lA-enhanced / 72-LIAH compositions. In the context of the present disclosure:• first generation / 72-LIAH compositions are as previously disclosed in Applicant’s International Patent Publication WO 2023 / 212824A1 (and related applications) the contents of which are hereby incorporated by reference; and• lA-enhanced / 72-LIAH compositions have an amorphous content of at least about 20%; and a median crystallite size of less than about 70 nm as detailed in the present disclosure.

[0100] lA-enhanced / 72-LIAH compositions and first generation / 72-LIAH compositions share some common attributes as their methods of manufacturing bothutilize an unconventional pH effect to induce the formation of a gel-like material. The present disclosure uses the term “ / 72-LIAH composition(s)” to refer to both lA-enhanced / 72-LIAH compositions and first generation / 72-LIAH compositions - particularly in differentiating from conventional LIAH compositions.

[0101] As reported in the present disclosure, the present inventors have developed protocols for manipulating key synthetic parameters during the formation and / or curing of the gel-like material to enhance the intrinsic amorphicity of the resultant compositions. Those skilled in the art will appreciate that while it may be desirable to reduce crystallite size to improve extraction efficiency, these improvements tend to be offset by poor physical robustness. The inventors of the present disclosure were able to offset this by leveraging the unconventional pH effect to advantageously influence crystalline-hydrate formation within the / -fe-LIAH compositions towards forming small crystallites, while also imbedding and advantageously distributing them throughout a substantially amorphous LIAH matrix to provide lA-enhanced / - / 2-LIAH compositions with improved extraction performance and desirable physical performance. The present inventors posited that desirable extraction-physical performance characteristics may be elicited by this approach to: (i) better support and / or position micro-arrays of discrete crystalline active sites; and / or (ii) impact the size and / or morphology of the crystallites. The present inventors further posited that enhancing intrinsic amorphicity may also attenuate or eliminate or reduce the need for exogenous binder by improving the intrinsic durability, shapeability, and / or ion-retention characteristics of the compositions they engender.

[0102] The lA-enhanced / 72-LIAH compositions of the present disclosure may be: (i) incorporated into sorbents for direct lithium extraction as described herein; (ii) synthesized by methods of manufacture as described herein; (iii) deployed in apparatus for recovering lithium from brine as set out herein; and / or (iv) deployed in methods for lithium recovery from brine as set out herein.

[0103] In the context of the present disclosure, the term “crystallite” refers to the detectable crystalline features of an / 72-LIAH composition, as characterized by X-ray diffraction (XRD), and / or scanning electron microscopy (SEM). In the context of the present disclosure, the terms “crystallization-hydrate” and “crystallization-hydrates” areused interchangeably and refer to matter with a detectable endothermic transition between about 270 °C and about 350 °C by differential scanning calorimetry (DSC). Crystall ization- hydrates may include water incorporated within or released from a crystal lattice, partial decomposition products of a crystal lattice, and / or complete decomposition products of a crystal lattice. In the context of the present disclosure, crystallization-hydrates are differentiated from “surface-hydrates”, as this term refers to matter with a detectable endothermic transition between about 30 °C and about 130 °C by DSC.

[0104] To improve the physical performance of LI AH compositions with small crystallite size, sorbent manufacturers may elect to add exogenous binders (e.g., alginates, biochars, biopolymers, carbonaceous ores, clays, polyvinyl alcohols, methyacrylates, graphenes, metal organic frameworks, nanotubes, polyphenols, synthetic polymers, polysaccharides, silicates, and / or combinations thereof). This may improve control of sorbent macro particle size and shape (e.g., allowing for better control of sorbent stability relative to physical process degradation, improved control of sorbent packing and operational pressures). However, this often leads to a decrease in sorbent performance. For example, binder material may occlude active sites and reduce lithium capacity and / or mass transfer kinetics. Additionally, even at relatively low binder loading (e.g. ~5 to ~30 wt%) there may be a significant increase to sorbent CAPEX.

[0105] As noted above, the lA-enhanced / 72-LIAH compositions of the present disclosure are composed of small, highly crystalline LIAH crystallites that are imbedded and advantageously distributed throughout a substantially amorphous LIAH matrix. Without being bound to any particular theory, a sorbent composition comprised of both small crystallites and amorphous content may provide the appropriate balance between extraction performance and physical durability, wherein amorphous regions within the tertiary structure of double-layer lithium hydroxide materials may act as a scaffold to support the small crystallites while maintaining larger macro particulate (e.g., agglomerate) size, thereby acting as an intrinsic binder. Control of desirable physical characteristics intrinsically, without the use of exogenous binder, may remove additional CAPEX requirements (e.g., additional chemicals for synthesis, process, purification, as well as shipping, storage, and disposal of said chemicals) and provides a sorbent composition that is uninhibited by additives. In the context of the present disclosure, theterm “intrinsic binder” refers to the amorphous character of lA-enhanced / 72-LIAH compositions, as characterized by XRD and SEM.

[0106] Without being bound to any particular theory, crystallization-hydrate incorporation within the lA-enhanced / 72-LIAH compositions of the present disclosure may impact d-spacing and / or lattice formation during crystallization. This process may explain why the gel-like material that is formed during manufacturing may be amenable to tailoring towards desirable properties {e.g. high lithium capacity, high lithium selectivity, high hardness, high physical durability under operating conditions, high chemical durability under operating conditions, large average particle size, and / or narrow particle size distribution) by selecting the appropriate reaction parameters {e.g., addition rates, mixing times), and curing protocols e.g., aging, rinsing, drying and sieving).

[0107] In the context of the present disclosure, the terms “crystallization-hydrate” and “crystallization-hydrates” are used interchangeably and refer to matter with an endothermic transition that is detectable between about 270 °C and about 350 °C by differential scanning calorimetry (DSC). Accordingly, the presence, absence, and / or degree of incorporation of crystallization-hydrates in a material may be readily determined by those skilled in the art. As those skilled in the art will appreciate, the crystallization process may result in highly regular {i.e., crystalline) as well as irregular {i.e., amorphous) material, both of which are anticipated to be comprised of crystalline-hydrates. The present disclosure provides teachings on determining molar ratios of crystallization- hydrates lithium from DSC data in combination with complementary characterizations including inductively-coupled plasma optical emission spectrometry (ICP-OES), thermogravimetric analysis (TGA), and / or X-ray diffraction (XRD).

[0108] In the context of the present disclosure, the term “crystallite” is used to describe / 72-LIAH crystalline formations ranging from about 1 nm to about 150 nm in length, as measured by scanning electron microscopy (SEM). As those skilled in the art may appreciate, improved extraction performance {e.g., capacity, mass transfer) is typically achieved by higher regularity in crystal structure and smaller crystallite size. For example, increased surface area may result in higher lithium transfer rate from brine to sorbent. Likewise, high crystallinity may provide improved access to sorbent active sites and increase sorbent lithium capacity.

[0109] In the context of the present disclosure, the terms “amorphous content” and “amorphicity” are used interchangeably to refer a quantifiable amount of / 72-LIAH material that possesses little or no long-range order. Amorphous content may generally refer to an absence of crystallinity or a limited amount of crystallinity. The amorphous content of a / 72-LIAH composition may be elucidated through XRD peak broadening and may be calculated as a percentage using XRD software. Amorphous content may also be observed in agglomerate features determined in SEM analysis of / 72-LIAH composition particulates {e.g., irregular formations, globular structure connecting smaller crystallites).

[0110] In the context of the present disclosure, a lithium containing solution may be a brine, such as one recovered from naturally occurring continental brine deposits. A lithium-containing solution may also be from fluid brine suspensions produced from hydraulic mining operations of geological formations, and / or from brines and wastewater produced from oil and gas production activities. The constitutions of lithium containing solutions suitable for use with the sorbents, apparatus, and / or methods of the present disclosure may vary widely. For example, lithium containing solutions having total dissolved solids (TDS) between about 50 ppm and about 5,000 ppm, between about 5,000 ppm and about 10,000 ppm, between about 10,000 ppm to about 100,000 ppm, between about 100,000 to about 250,000 ppm, or between about 250,000 ppm to about 500,000 ppm may be suitable. With respect to cation loading, suitable lithium containing solutions may comprise varying concentrations of lithium, sodium, potassium, calcium, magnesium, or combinations thereof. In the context of the present disclosure, the term “brine” may refer to a natural brine, a synthetic brine, or a combination thereof. In the context of the present disclosure, the term “ion” is defined as a metal ion of any valency including, but not limited to, lithium, potassium, calcium, magnesium, manganese, iron, zinc, cobalt, nickel, titanium, aluminum, tin, gallium, silver, gold, copper, strontium, cadmium, or a combination thereof. In the context of the present disclosure, the term “lithium” is used broadly to encompass lithium ions in solution, adsorbed to a surface, and in chemical compositions such as lithium chloride, lithium carbonate, and lithium hydroxide. Those skilled in the art will recognize that lithium ions may take a variety of forms, all of which fall within the scope of the present disclosure. For example, lithium ions may be hydrated, participating in coordinated ion pairs, retained in interstitial sites, suspended in colloid forms, and the like.

[0111] These and other teachings, objects, features, examples, ranges, thresholds, and advantages of the present disclosure will be apparent to those skilled in the art having regard to the following description of particular embodiments of the lA-enhanced / 72-LIAH compositions of the present disclosure with reference to the appended drawings - including their incorporation into a sorbent for recovering lithium from brine, methods fortheir manufacture, their incorporation into apparatus for recovering lithium from brine, and their use in methods for recovering lithium from brine - without limitation to the scope of the appended claims.Characterization and Analysis of / 72-LIAH compositions

[0112] The lA-enhanced / 72-LIAH compositions of the present disclosure are an advancement from the first generation / 72-LIAH compositions reported previously in Applicant’s International Publication WO 2023 / 212824A1 (and related applications). In the sections below, select results and discussions enable those skilled in the art to differentiate between the lA-enhanced / 72-LIAH compositions of the present disclosure from the first generation / 72-LIAH compositions reported previously. Other results and discussions are included to enable those skilled in the art to differentiate between conventional LIAH compositions and / 72-LIAH compositions - including the lA-enhanced / 72-LIAH compositions of the present disclosure. Characterization and analysis of the lA-enhanced / 72-LIAH compositions of the present disclosure need not be limited to the analytical techniques set out below, and those skilled in the art will appreciate that other characterization techniques may supplement, support, or replace one or more of the foregoing analyses without departing from the scope of the present disclosure.

[0113] As will be appreciated by those skilled in the art, co-precipitation reactions at industrial scale typically employ aluminum sulfate- or aluminum nitrate solutions as the aluminum source. These soluble forms do not pose significant corrosion concerns when used with typical stainless-steel coatings and materials, as used in equipment that enables high temperature, high pressure, high strength processing at industrial scale. However, use of said sulfate-based aluminum solutions may result in impurities issues {e.g., iron) and pose health and safety risks during high-temperature processing (e.g., generation of toxic sulfur oxides). Nitrate-based aluminum solutions can be significantly purified, enabling lower temperature processing, and generation of nitrogen oxides is relativelyeasier to handle at industrial scale. During- or after processing, nitric acid can commonly be regenerated and recycled from co-precipitation reactions to improve environmental impacts and overall economic efficiencies.

[0114] Aluminum chloride by contrast can be very corrosive to metals, particularly in the case of chloride stress-corrosion cracking, which limits applicability of austenitic steels at elevated temperatures. Higher grade materials can be used, which quickly can ramp up capital expenditures. Impurities (e.g., iron) may be difficult to remove. Considerable amounts of sodium chloride, although benign, must be managed from the co-precipitation reactions. Application of aluminum chloride chemistry is not common at industrial scale.

[0115] As with the first generation / 72-LIAH compositions reported previously, the endothermic transitions of an lA-enhanced / 72-LIAH composition may differ from those of a conventional LIAH composition and may be determined by DSC. Those skilled in the art will appreciate the particulars of routine DSC characterizations as used in the present disclosure. Figure 1 shows a DSC graph 100 depicting relative enthalpic variation as a function of temperature for a conventional LIAH composition 111 , and an / 72-LIAH composition 121. Representative of / 72-LIAH compositions in general (including the lA-enhanced / 72-LIAH compositions of the present disclosure), a characteristic enthalpic event 122 is observed with a distinctive and characteristic onset temperature, about 270 °C, as compared to that of the conventional LIAH composition 112, which is observed with an onset temperature of about 200 °C. In Figure 1 , Surface-hydrate loss 105 may be noted by wide, low intensity enthalpic events centered at about 80 °C for both materials.

[0116] The thermal decomposition patterns of / 72-LIAH compositions in general (including the lA-enhanced / 72-LIAH compositions of the present disclosure) may be determined by TGA. Those skilled in the art will appreciate the particulars of routine TGA characterizations as used in the context of the present disclosure. Figure 2 shows a normalized TGA plot 200 depicting sample weight changes (expressed as a relative percent) as a function of temperature for a series of / 72-LIAH compositions. Across the series, and representative of the / 72-LIAH compositions in general (including the lA-enhanced / 72-LIAH compositions of the present disclosure), a major decomposition event 211 may be seen at an onset beginning at about 270 °C and offset ending at about320 °C. This decomposition event is complementary to the DSC characteristic enthalpic event in Figure 1. Similarly, surface-hydrate loss as identified by DSC in Figure 1 is also detectable in TGA plot 200 as indicated by reference number 212.

[0117] The crystal diffraction pattern of an / 72-LIAH composition may be determined by XRD. Those skilled in the art will appreciate the particulars of routine XRD characterizations as used in the context of the present disclosure. Figure 3 shows an overlay 300 of three XRD diffractograms. Two of the XRD diffractograms (311 and 321) are derived from / 72-LIAH compositions and the other (331) is derived from a conventional LIAH composition that was prepared by a Gibbsite impregnation method. The primary characteristic peak of the / 72-LIAH compositions is at about 11.5 °20 (312). Additional characteristic peaks of the / 72-LIAH compositions 313, 314, and 315, are at about 20.1 °20, 23.1 °20, about 35.0 °20, and about 35.7 °20, respectively. The primary characteristic peak of the conventional LIAH composition is at about 18.2 °20 (332). This peak is conspicuously absent in the patterns of the / 72-LIAH compositions.

[0118] XRD analysis within the present disclosure assumes use of a copper X-ray source. Those skilled in the art will appreciate the expected change in peak position ( / .e., degrees 2-theta) anticipated from using an alternative XRD source material.

[0119] As with the first generation / 72-LIAH compositions reported previously, the molecular formula of an lA-enhanced / 72-LIAH composition may be represented by Formula 1 and may be determined using manufacturing information and subsequent characterization data described in the present disclosure:LiaX mAI(OH)3 nH2Ocr Formula 1 wherein: a is about 1 ;X is a mono-valent anion; m is between about 1.9 and about 3.6; n is between about 2.1 and about 4.3; andH2Ocr specifies crystallization-hydrate.The following discussion teaches those skilled in the art how to determine the inputs of Formula 1 using an archetypal / 72-LIAH composition as an example.

[0120] The use of lithium chloride identifies integer “a” as 1 and mono-valent anion “X” as chloride. Thus, the partial molecular formula may initially be determined to be: LiCl mAI(OH)3nH2OCT.

[0121] Elemental composition data may be determined by ICP-OES. Those skilled in the art will appreciate the particulars of routine ICP-OES characterizations as used in the context of the present disclosure. Elemental composition data for an archetypal / 72-LIAH composition is summarized in Table 1.Table 1: Archetypal / 72-LIAH elemental composition as analyzed by ICP-OES.

[0122] The ratio of aluminum to lithium, normalizing the molar concentration of lithium to 1 , is thus determined to be 2.26 : 1. Having normalized the ratio relative to lithium, the aluminum ratio may be input into Formula 1 as “m”, and the partial molecular formula may be further described : LiCI-2.3AI(OH)3 nH2OCT.

[0123] In the context of the present disclosure, the crystallization-hydrate : lithium ratio of a LIAH composition may be determined as follows.

[0124] TGA data may be used to differentiate specific heating zones within which surface-hydrates and crystallization-hydrates are individually lost during the analysis of the archetypal / 72-LIAH composition. Table 2 summarizes TGA data at two specific timepoints for an archetypal / 72-LIAH composition, which describe a temperature rangeacross which crystallization-hydrates may be observed. In the context of the present disclosure, relative TGA mass values may be used to determine relative mass loss, in percent, specific to crystallization-hydrates, as outlined in Formula 2:Rel. Losscry= Rel. Mass120°c~ R l- ^ass35orjc Formula 2 wherein:Rel. Massac is the TGA measurement of relative mass at 120 °C; andRel. Mass35o°c is the TGA measurement of relative mass at 350 °C.

[0125] With respect to the archetypal / 72-LIAH composition and its TGA data of Table 2, the relative mass loss of crystallization-hydrates was determined to be 24.6%.

[0126] In the context of the present disclosure, crystallization-hydrate : lithium molar ratios may be calculated from TGA data and ICP-OES data by mass balance using Formula 3. The ICP-OES data is first assessed to provide the aluminum : lithium molar ratio, which is then used in Formula 3. Alternatively, if desired, similar ratios may be determined using mass values as derived from these data. The archetypal / 72-LIAH composition was determined to have an aluminum : lithium ratio of about 2.3 : 1.0 based on the data in Table 1.

[0127] Formula swherein:R,l is the molar ratio of lithium, which is normalized to 1 ;R,n is the molar ratio of aluminum trihydroxide relative to lithium; / WI / I is the molecular weight of the species in question;MWuci = 42.40 g / mol;MWAIOH3 = 78.00 g / mol;MWH2O = 18.02 g / mol; andRel. Losscry is the relative percent mass loss of crystallization-hydrate.

[0128] With respect to the archetypal / 72-LIAH composition and its TGA data, the relative mass loss of crystallization-hydrates was determined to be 2.5. Accordingly, the specific molecular formula for the archetypal / 72-LIAH composition, having identified the final integer “n”, may be expressed fully. Formula 1 is thus determined as:LiCI-2.3 AI(OH)3-2.5 H2OCfy

[0129] The impact of the loss crystallization-hydrates on / 72-LIAH compositions in general (including the lA-enhanced / 72-LIAH compositions of the present disclosure) may be determined by a suite of analytical techniques as outline below.

[0130] Figure 4 shows a Fourier transform infrared (FTIR) spectra overlay 400 of a / 72-LIAH composition before 411 and after 421 high temperature drying. Those skilled in the art will appreciate the particulars of routine FTIR characterizations as used in the present disclosure. Individual FTIR bands have been identified for the purpose of this discussion and are assigned to their respective material. For brevity, the x-axis is truncated by a caesura 402. General -OH bond stretch absorbances may be noted for both materials with a strong relative absorbance shown for the / 72-LIAH composition before high temperature drying 415 and a reduced absorbance for the / 72-LIAH composition after high temperature drying 425. Absorbance bands indicative of aluminum bonding are identified for the / 72-LIAH composition before high temperature drying with reference numerals 416 and 417. After high temperature drying, the / 72-LIAH composition shows distinct loss of the Al-O- stretch band 426, and a reduced AI-OH bend band 427. Without being bound to any particular theory, the changes observed for the Al-O- bondingbands suggest a significant loss of crystallinity as a result of high temperature drying. The loss of crystallinity associated with high temperature drying may also be observed in DSC data set out above. The endotherm 121 observed in Figure 1 lacks indications of a subsequent recrystallization event, as observed in peak shape and graph trends, such as the symmetrical, Gaussian shape and the lack of sharp slope resultant of supercooling recrystallization events.Comparative analysis of lA-enhanced / 72-LIAH compositions vs first generation / 72-LIAH compositions

[0131] In this section, select results and discussions further enable those skilled in the art to differentiate between the lA-enhanced / 72-LIAH compositions of the present disclosure from the first generation / 72-LIAH compositions reported previously.

[0132] Figure 5 shows an overlay 500 of two XRD patterns. Comparison of the XRD d iff ractog rams may be used to assess the relative amounts of intrinsic binder in / 72-LIAH compositions. Those skilled in the art will appreciate the particulars of routine XRD characterizations as used in the present disclosure. The powder diffraction pattern for lA-enhanced / 72-LIAH composition 502 and first generation LIAH composition 501 are overlaid in diffractogram 500, as determined with background correction. Therein, the primary peaks of both patterns 501 and 502 match well, indicating little to no change to the overall crystal structure. However, those skilled in the art will appreciate the subtleties relating to analysis of the data presented. As shown, the first generation / 72-LIAH composition pattern 501 is characterized by sharp, narrow, well-defined peaks, especially at about 11.5 degrees 20 as well as about 20.5 and 23.0 degrees 20 typical for materials with good long range order, and therefore displays high crystallinity. In contrast, the lA-enhanced / 72-LIAH pattern 502 depicts lower overall peak intensities and peak broadening, often characteristic of materials with a lower degree of order. This decrease in order may be caused by the presence of crystalline defects, irregular crystallization, smaller grain sizes, or a combination thereof. An increase of amorphous character may be noted in both the broadening of the characteristic crystalline peaks, an overall increase in background signal, or a combination thereof. Depending on the specific crystalline sample, and the relative variability in amorphous content between samples of similarsynthetic design, changes in amorphicity may or may not be visible to the naked eye.Table 3 outlines amorphicity values for the same.

[0133] Table 3: Amorphous content of an lA-enhanced / 72-LIAH composition and a first generation / 72-LIAH composition as determined from XRD analysis.

[0134] Figure 6 shows scanning electron microscopic (SEM) images 600 of both a first generation / 72-LIAH composition (Panel 6A) and an lA-enhanced / 72-LIAH composition (Panel 6B). Those skilled in the art will appreciate the particulars of routine SEM characterizations as used in the present disclosure. Individual crystallites (611 and 621) are readily observable for the first generation / 72-LIAH composition and the lA-enhanced / 72-LIAH composition, respectively. Likewise, agglomerates 612 and 622 are readily observable for the first generation / 72-LIAH composition and the lA-enhanced / 72-LIAH composition, respectively. The crystallites 621 of the lA-enhanced / 72-LIAH composition are significantly smaller than the crystallites 611 of the first generation / 72-LIAH composition. The agglomerates 622 of the lA-enhanced / 72-LIAH compositions have higher irregularity than the agglomerates 612 of the first generation / 72-LIAH composition. This may result from tighter, more random packing of the crystallites along the sorbent surface in the lA-enhanced / 72-LIAH composition, and this improved agglomeration may result from the higher percentage of amorphous content acting as a binder. An excerpt of representative SEM analysis of the lA-enhanced / 72-LIAH composition and the first generation / 72-LIAH composition is provided in Table 4.

[0135] Table 4: SEM analysis of an lA-enhanced / 72-LIAH composition and a first generation / 72-LIAH composition.

[0136] As those skilled in the art will appreciate, there is a consistent need to avoid sampling bias during routine SEM analysis. A typical SEM sample is loaded onto aspecimen stub e.g., 15mm or 12.5 mm or 8 mm in diameter) in a monolayer, such that all particulate is evenly distributed. Finely distributed materials may require less than 10 mg of sample for a single SEM analysis. Care must be taken to ensure that sampling bias is reduced by all means possible. For example, preparation of sample for analysis from materials of large size relative to the instrument specimen stub {e.g., agglomerates, extrudates, shaped and / or moulded particulates, slurries, manufacturing process cakes) may require size reduction of the material. Efforts to decrease material size for analysis may significantly change the morphology of the sample, such that the SEM images generated during analysis are no longer representative of the original material. Similarly, subsampling must be implemented in a manner that allows for the analyzed sample to be representative of the original material lot. For example, manufacturing lines that produce solid material over a large particle size distribution (e.g., ranging from < 1 nm to > 10,000 nm) should not select a singular material from only one particle size grouping for SEM analysis. An ideal SEM batch analysis should include repeated sub-sampling (e.g., n > 3), and should include as many sub-sample groupings as there are distinct morphologies in the material. For example, a material with three distinct particle size groupings should include three sub-sample groups. Similarly, analysis of a singular sample must be conducted in a manner that allows a singular SEM image to be representative of the entire sample loaded onto the specimen stub. For example, analysis of crystallite features (e.g., about 1 to 50 nm) in a single SEM image should be confirmed to be present in multiple additional images (e.g., n > 3) from the same specimen stub at different locations.

[0137] As those skilled in the art will appreciate, quantification of the amorphous content of crystalline samples requires significant attention to the preparation of samples for analysis. Production of solids on scale may result in large particulate sizes (e.g., 5,000 nm) which are inherently unsuitable for standard analysis by XRD. XRD sample holders for typical analysis (e.g., diffractometers using Bragg- Brentano geometry) have powder wells of about 30 mm in diameter and must contain a powder sample thickness of between about 50 pm and about 1 ,500 pm. Generally, powders with a particle size of < 20 pm may be preferred. While it is necessary to treat large particulate samples prior to analysis (e.g., grinding, milling, micronizing) efforts must be made to limit this treatment to a minimized amount of physical force for a minimized amount of time, only as required to produce a usable powder. Excessive sample treatment involving unnecessary applicationof force {e.g., beyond the requirements to create a powder sample) may break down the crystallinity of said sample and result in an artificially induced increase in amorphicity.

[0138] As discussed herein, TGA data may be used to assess the relative amounts of crystalline hydrates in / 72-LIAH compositions. While the characteristic decomposition event as shown in Figure 2 may display the same characteristic shape for all / 72-LIAH compositions, the specific crystalline-hydrate masses may change in accordance with changes to the manufacturing process. Table 5 compares the crystalline- hydrate mass of an archetypal lA-enhanced / 72-LIAH composition with that of a first generation / 72-LIAH composition. Without being bound to any particular theory, an increase in the relative amount of crystallinity {e.g., increase in number of crystallites) may be indicative of a higher crystalline-hydrate value. The relative TGA crystalline-hydrate mass values were calculated using Formula 2.

[0139] Table 5: TGA relative mass readings for an lA-enhanced / 72-LIAH composition and a first generation / 72-L / A / 7 composition.

[0140] An lA-enhanced / 72-LIAH composition and a first generation / 72-LIAH composition were evaluated for hardness using a hydraulic press set to produce 1% fines. Those skilled in the art will appreciate the particulars of routine hardness analyses as used in the present disclosure. The hardness results for the lA-enhanced / 72-LIAH composition and the first generation / 72-LIAH composition are set out in Table 6.

[0141] Table 6: Hardness test results for an lA-enhanced / 72-LIAH composition and a first generation / 72-LIAH composition.

[0142] The surface areas of an lA-enhanced / 72-LIAH composition and a first generation / 72-LIAH composition were evaluated using Brunauer, Emmett and Teller(BET) theory. Those skilled in the art will appreciate the particulars of routine BET analyses as used in the present disclosure. Nitrogen gas was used for the evaluation, resulting in the specific surface area values listed in Table 7. The true density of the lA-enhanced / 72-LIAH composition and the first generation / 72-LIAH composition was determined by densometer.

[0143] Table 7: Specific surface area results for an lA-enhanced / 72-LIAH composition and a first generation / 72-LIAH composition.

[0144] Particle size distributions (PSD) were obtained for an lA-enhanced / 72-LI AH composition slurry and a first generation / 72-LIAH composition slurry using laser dispersion in water. Those skilled in the art will appreciate the particulars of routine PSD analyses as used in the present disclosure. Table 8 sets out the particle fractions determined for the lA-enhanced / 72-LIAH composition and the first generation / 72-LIAH composition. Improved agglomeration {e.g., proper distribution of crystallites, even distribution of crystallites, reduced inclusions and open space) may result in larger particle size fractions as observed in the d50 and d90 size fractions. This improved agglomeration may result from the inclusion of additional intrinsic binder, allowing for better macro particulate size control and may result in improved physical stability when immersed in aqueous solutions.

[0145] Table 8: Particle size distribution results for an lA-enhanced / 72-LIAH composition and a first generation / 72-LIAH composition

[0146] Turbidity measurements were obtained for an lA-enhanced / 72-LIAH composition and a first generation / 72-LIAH composition. Those skilled in the art will appreciate the particulars of routine turbidity analyses as used in the present disclosure. Approximately 0.5 g of sorbent, pre-sieved to isolate between about 2,000 pm and about 2,750 pm particle fractions, was added to about 100 mL of de-ionized water and mixed at 300 RPM for about 5 minutes. Turbidity samples were withdrawn from the surface of theactively stirring solution and aliquoted to vials for testing, each of which was mixed by repeated inversion prior to analysis. The turbidity results for the lA-enhanced / 72-LIAH composition and the first-generation / 72-LIAH composition are set out in Table 9. The results indicate that structural and chemical robustness of the lA-enhanced / 72-LIAH composition were enhanced relative to the first generation / 72-LIAH-1 composition, which may correlate with enhanced chemical durability as a sorbent for lithium recovery from brine.

[0147] Table 9: Turbidity measurements for a suspension comprising an lA-enhanced / 72-LIAH composition and a suspension comprising a first generation / 72-LIAH composition

[0148] Additional structural robustness characteristics may be evaluated by assessment of / 72-LIAH compositions during the manufacturing process (e.g., in-process testing). Gel strength measurements were obtained for an lA-enhanced / 72-LIAH composition and a first generation / 72-LIAH composition, and the results are set out in Table 10. The gel strength for the lA-enhanced / 72-LIAH composition is shown to be significantly higher than that of the first generation / 72-LIAH composition. Without being bound to any particular theory, the improved crystallization processes of the present disclosure, designed to further increase the physical robustness of the final sorbent composition, are shown to be descendent of a stronger gel formation.

[0149] Table 10: Gel strength measurements during preparation of an lA-enhanced / 72-LIAH composition and a first generation / 72-LIAH compositionLithium extraction performance of lA-enhanced / 72-LIAH compositions

[0150] Lithium uptake capacity was determined for an lA-enhanced / 72-LIAH composition and a conventional LIAH composition using a bench scale column apparatus. The apparatus used a lab stand and a jacketed glass column with an inner diameter ofabout 3.2 cm, a height of about 20 cm, and a frit to minimize loss of particles. Heating for the column was provided by an external circulating water bath with a set operating temperature. In each case, a pre-weighed mass of test composition (between about 50 g and about 70 g) at a predetermined particle size range was transferred to the column. The packed sorbent height was determined after pumping water or eluent (200 ppm Li solution) through the column using the operating flow path (top down). To prepare the test composition for adsorption, an initial elution was performed using the eluent to a total of 10 bed volumes to remove entrained lithium. Following this, the adsorption and elution stages were performed at elevated temperatures between 40 °C to 80 °C using a prepared synthetic feed brine and eluent respectively. The synthetic brine included the species set out in Table 11 at the noted concentrations as determined via ICP-OES or inductively coupled plasma mass spectrometry (ICP-MS).

[0151] Table 11 : Composition of a brine feed used in evaluating an lA-enhanced / 72-LIAH composition and a conventional LIAH composition

[0152] Processing volumes for the adsorption stage were calculated using a target maximum lithium capacity of 10 mg / g based on the amount of sorbent weighed and packed into the column - this correlated to between 5 to 10 bed volumes. Flow rates were adjusted such that the flux rate of fluid through the sorbent was between 300 and 400 L / rm / hour. To determine the performance of the test compositions during the adsorption stage, samples were obtained from the outlet (at the bottom of the column) at regular time intervals and the composition of each sample determined via ICP-OES.

[0153] The lithium uptake capacity was determined by applying Formula 4._ Absorbed Lihium > [Li]Initial- [Li]Final) x VolBrineFormula 4LlCap -M~M1‘Sorbent1‘SorbentWherein:Licap = lithium uptake capacity, in mg / g;Msorsbent= mass of sorbent, in g;Adsorbed Lithium = total lithium adsorbed, in mg;[Li]initiai: initial lithium concentration, in mg / L;[Lijrinai: initial lithium concentration, in mg / L; andVolBrine: volume of brine tested, in L.

[0154] The lA-enhanced / 72-LIAH compositions of the present disclosure were found to achieve between about 9.5 mg / mL and about 12.0 mg / mL lithium uptake capacity after repeated use extracting lithium from salar brines.

[0155] Figure 7 displays an excerpt of process monitoring data 700 for an lA-enhanced / 72-LIAH composition when used for continuous, cyclical DLE. The method for recovering lithium was in accordance with an embodiment of the present disclosure, as was the apparatus. In Figure 7, the x-axis is truncated by a caesura (705 and 706) where required for brevity. The typical cycle 711 displays the lithium concentration variation first as brine is loaded into the system, and then as lithium is adsorbed onto the lA-enhanced / 72-LIAH composition as loaded in the column. Column performance was maintained through successive cycles, such that chemical durability and / or physical durability may be evaluated. Samples were obtained from the outlet (at the bottom of the column) at regular time intervals and the composition of each sample determined via ICP-OES. Elutions were performed using a volume of eluent equivalent to the feed brine and at flux rates corresponding to 300 to 800 L / r / hour. Sampling was performed similarly to that in the adsorption stage. For sorbent evaluation, two to three adsorption / elution cycles were performed using the synthetic feed prior to evaluation using a real brine sample for comparison.

[0156] Following repeated adsorption and extraction cycles using salar brine, the lA-enhanced / 72-LIAH compositions of the present disclosure were found to have no change in lithium capacity after extensive runtime (e.g., after more than about 400 hours), indicating no negative impact to the sorbent performance and / or physical structure.Methods of manufacturing lA-enhanced / 72-LIAH compositions

[0157] In an archetypal example, an lA-enhanced / 72-LIAH composition was manufactured by the following method. Lithium chloride (30.0 kg) was dissolved into a solution of AlCh (698.9 kg, 25-30%) and combined by overhead stirring with constant recirculation until the lithium chloride was completely dissolved, such that the molar ratio of Li : Al was about 1 : 2. With a mixing rate set to about 20 rpm and a recirculation rate of 50 mg / min, an aliquot of a NaOH solution (339.6 kg, 50%) was combined with an aliquot of water (410.4 L). The pH of the NaOH solution was monitored as it was increased to greater than about 12. With continued mixing, the LiCI / AICh solution was added at a rate of about 3 L / min, and the reaction mixture was observed to thicken as the pH decreased. A gel-like material formed upon the total addition of the LiCI / AICh solution, and the pH decreased to less than about 2.0. The slurry was agitated for an additional 20 minutes. The slurry was neutralized by iterative addition of aliquots of about 4.0 L of the 50% NaOH solution, and the pH was monitored between additions. After the pH had risen above about 2.5 the iterative addition of the aliquots of 50% NaOH solution were reduced to about 0.3 L. The slurry further thickened at pH above about 3.5, after which the iterative addition of the aliquots of 50% NaOH solution were reduced to about 0.1 L and a minimum mixing time of 10 min was applied between aliquots. Viscosity was monitored indirectly, from recirculation pump pressure, and confirmed via sampling. Neutralization was halted once the pH reached 5.8 - 6.2 and mixing continued for an additional 20 minutes. About 500 g of the resulting composition was transferred to a centrifuge decanter, where it was heated at about 60 °C, circulated at a pumping rate of 17 rpm, and centrifuged for a period of 10 min. The centrate was sampled for moisture content and removed once the moisture was less than about 70% by moisture analyzer and the salt content was less than about 60% by ICP-OES. This provided a wet cake, which was transferred onto an IR heat dryer belt and distributed evenly. Heating was applied such that the surface temperature was maintained between 90 °C and 110 °C. The cake bed was scraped and resettled every two hours. Solids were monitored by subsampling and testing with a moisture analyzer. After the average moisture content was less than about 20%, heating was discontinued and the mass loss at 100 °C was confirmed to be less than about 15% by TGA. The dried composition was then rinsed iteratively, in 15 kg aliquots. The dried composition was transferred to a rinsing tank containing 200 L of water and agitated at 260 rpm for 20 min,then sieved with a 500 nm mesh screen. The rinsed and sieved composition was transferred onto an IR heat dryer belt and distributed evenly. Heating was applied such that the surface temperature was maintained at about 130 °C for between 6 and 8 hours. Solids were monitored by subsampling and testing with a moisture analyzer. After the average moisture content was less than about 15%, heating was discontinued. The composition was then manually sieved and separated to obtain a particle fraction of between about 1200 nm and about 3500 nm, after which the lA-enhanced / 72-LIAH composition was characterized as described herein.

[0158] As will be appreciated by those skilled in the art, drying of solids at industrial scale may be achieved by convective methods (e.g., belt, band, or tunnel dryers; rotary dryers; tray dryers; fluid bed dryers, pneumatic conveying dryers; flash dryers; and / or spray dryers), said convective methods being either direct with respect to the application of heat, or indirect (e.g., using a heat transfer medium such as steam, or inert gas), conductive methods (e.g., using vacuum dryers, continuous plate dryers, paddle dryers, ribbon dryers, freeze dryers, and / or thin film evaporators), or any combination thereof.

[0159] In an embodiment of the present disclosure, as the reaction mixture approaches the minima of the pH transition associated with the addition of the LiCI / AICh mixture, and the gel-like material forms, the mixing time may be selected to balance: (i) increasing homogeneity, and thus modulate the size of individual crystallites and overall strength of the gel; with (ii) reducing formation of carbonates generated from long term atmospheric exposure; and / or (iii) reducing impurity formation. In an embodiment of the present disclosure, gel strength may be increased by modulating the mixing rate, increasing one or more reactant concentrations, and / or altering the reagent addition order relative to stoichiometric control. An increase in gel strength may correlate to a larger amount of crystallization-hydrates in the lA-enhanced / 72-LIAH composition.Apparatus and methods for recovering lithium from brine using lA-enhanced / 72-LIAH compositions

[0160] Figure 8 shows an apparatus 800 for recovering lithium from a lithium containing solution in accordance with an embodiment of the present disclosure. Figure 8 also shows a method 850 for recovering lithium from a lithium-containing solution inaccordance with an embodiment of the present disclosure. Apparatus 800 is configured to execute method 850 using a lead, guard, elution column configuration, wherein one or more of the columns comprises an lA-enhanced / 72-LIAH composition in accordance with the present disclosure. The lead column is indicated by cross hatching, the guard column is indicated by horizonal hatching, and the elution column is indicated by vertical hatching. During operation, these columns are rotated through an extraction cycle. This process is depicted in Figure 8, where apparatus 800 comprises columns 808, 810, and 812, which process brines according to steps 852, 854, and 856 as follows.

[0161] At step 852, column 808 is adsorbing lithium while column 810 acts as a guard column to collect any residual lithium before depleted brine is discharged as a raffinate which may be recycled for further lithium extraction, further treated, stored, or disposed of. Also at step 802, an eluent is flowed through column 812 to desorb lithium adsorbed during a previous cycle. This provides a lithium-enhanced eluate, which may be passed to a water recovery technology.

[0162] At step 854, column 810 is reconfigured from guard column to lead column. Column 810 receives brine and adsorbs lithium therefrom. Also at step 854, column 812 is reconfigured from elution column to guard column, and it adsorbs residual lithium. Also at step 854, column 808 is reconfigured from lead column to elution column, and it desorbs lithium retained from step 852.

[0163] At step 856, column 812 is reconfigured from guard column to lead column. Column 812 receives brine and adsorbs lithium therefrom. Also at step 856, column 808 is reconfigured from elution column to guard column, and it adsorbs residual lithium. Also at step 856, column 810 is reconfigured from lead column to elution column, and it desorbs lithium retained from step 854.

[0164] Steps 852, 854, and 856 may be cycled by adjusting a valve manifold (or an alternative means for fluid control) to direct flows of brine, eluent, and the like.

[0165] As will be appreciated by those skilled in the art, apparatus 800 is one of many configurations that may be suitable for recovering lithium in the context of the present disclosure (likewise for method 850), as apparatus and methods for recoveringlithium from lithium containing solutions are generally known to those skilled in the art. Those skilled in the art will appreciate the science and engineering fundamentals (e.g. equilibrium and mass transfer considerations) associated with using sorbents in such apparatus and / or methods, as evidenced by: Gableman, A., “Absorption Basics: Part 1 ,” Chemical Engineering Progress, 113 (7), pp 48-53 (July 2017), the contents of which are herein incorporated by reference. For example, apparatus for lithium recovery in accordance with the present disclosure may be configured as sequential flow systems (also referred to as a "daisy chain" flow systems) configured in parallel, in series or in combinations of parallel and series, flowing either in upflow or downflow modes. Likewise, apparatus for lithium recovery in accordance with the present disclosure may employ countercurrent extraction. In countercurrent extraction, the eluent is pumped countercurrent to sorbent advance for example by way of an indexed multi-port valve system and / or a carousel of sorbent containers. Apparatus for lithium recovery in accordance with the present disclosure may be configured to operate under a variety of temperature and pressure conditions. For example, apparatus for lithium recovery in accordance with the present disclosure may operate at temperatures less than about 60 "C, between about 60 "C and about 100 C, and / or greater than about 100 C.Further description of embodiments of the present disclosure

[0166] An aspect of the present disclosure relates to a sorbent for recovering lithium from a lithium containing solution, the sorbent comprising an lA-enhanced / 72-LIAH composition having a crystallization-hydrate : lithium molar ratio of at least about 2.1 : 1.0. In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition may include a single compound or a plurality of compounds. In an embodiment of the present disclosure, the crystallization-hydrate : lithium molar ratio of the lA-enhanced / 72-LIAH composition may be between about 2.1 : 1.0 and about 4.3 : 1.0. In an embodiment of the present disclosure, the crystallization-hydrate : lithium molar ratio of the lA-enhanced / 72-LIAH composition may be between about 2.4: 1 .0 and about 2.9: 1.0. In an embodiment of the present disclosure, the crystallization-hydrate : lithium molar ratio of the lA-enhanced / 72-LIAH composition may be less than about 4.3 : 1.0. In an embodiment of the present disclosure, the crystallization-hydrate : lithium molar ratio of the lA-enhanced / 72-LIAH composition may between about 2.9: 1.0 and about 4.0: 1.0. Those skilled in theart, having benefited from the teaching of the present disclosure, will understand how to tailor manufacturing conditions to provide lA-enhanced / 72-LIAH compositions within the noted ranges. For example, the following parameters may be controlled to induce higher crystal lization-hydrate : lithium molar ratios (reference numerals related to the method of manufacturing steps described herein):• decreasing the concentration of the hydroxide solution used in step (i) and / or step (iii) and or step (v);• reducing the pH of the reaction mixture below about 2.0 (for example to about 3.0 or about 1.5) in step (i);• perform high-shear mixing during step (i);• reducing the lithium concentration relative to the aluminum concentration in step (i); and• reducing the reaction time for step (i) and / or step (ii).

[0167] In an embodiment of the present disclosure, the crystallization-hydrate : lithium molar ratio of an lA-enhanced / 72-LIAH composition may be determined from DSC, ICP-OES, TGA, or a combination thereof. Analysis of the lA-enhanced H2-UM-\ composition of the present disclosure need not be limited to these analytical techniques. Those skilled in the art will appreciate that other characterization techniques may supplement, support, or replace one or more of the foregoing analyses without departing from the scope of the present disclosure. In the context of the present disclosure, analysis by DSC may require samples to be loaded into aluminum transfer crucibles prior to analysis. Each crucible may be capped, and each cap may be perforated with a sharp tip to allow for the evolution of gases throughout the experiment. During analysis, the samples may be treated to a constant rate of increasing temperature, from ambient to 450 °C. Experimental data may be provided as enthalpic changes during heating. In the context of the present disclosure, samples for TGA may be loaded into aluminum transfer crucibles. During analysis the samples may be treated to a constant rate of increasing temperature, from ambient to 450 °C. Experimental data may be provided as relative mass loss (%) during heating. In the context of the present disclosure, prior to elemental analysis by ICP-OES (or, alternatively, ICP-MS) samples may be digested with acid in plasticware and diluted for analysis with deionized water. In the context of the present disclosure, FTIR samples may be prepared by grinding materials to a powder, after which they may bemounted on an FTIR spectrometer equipped with an attenuated total reflectance (ATR) accessory. Spectra may be acquired over the range of 4000-400 cm-1. In the context of the present disclosure, samples to be analyzed by XRD may be delumped and mounted on X-ray transparent supports (e.g. single crystal silicon) and analyzed using Bragg- Brentano instrumental geometry. In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition may be characterized by 20 reflectance peaks at approximately 11.5 °20, 20.1 °20, 23.1 °20, 35.0 °20, and 35.7 °20, or a combination thereof via XRD. Likewise, lA-enhanced / 72-LIAH compositions of the present disclosure may be characterized by the absence of reflectance peaks at 18.2 °20, via XRD.

[0168] In an embodiment of the present disclosure, the amorphous content of the lA-enhanced / 72-LIAH composition is between about 20% and about 140%. In an embodiment of the present disclosure, the amorphous content of the lA-enhanced / 72-LIAH composition is between about 23% and about 35%. In an embodiment of the present disclosure, the amorphous content of the lA-enhanced / 72-LIAH composition is between about 26% and about 31%. Those skilled in the art, having benefited from the teaching of the present disclosure, will understand how to tailor manufacturing conditions to provide lA-enhanced / 72-LIAH compositions within the noted ranges. For example, the following parameters may be controlled to induce high levels of amorphicity:• reducing the hydroxide : aluminum ratio in step (i);• increasing the target pH to about 4.5 to about 5.5 in step (i);• increasing the dilution of the reaction mixture in step (i), and / or step (i), and / or step (v);• increasing the reaction mixture temperature in step (i);• reducing the reaction time at step (ii), and / or step (v), and• increasing the temperature and / or time of aging at step (iii).

[0169] In an embodiment of the present disclosure, the amorphous content of the lA-enhanced / 72-LIAH composition is determined by X-ray diffraction (XRD).

[0170] In an embodiment of the present disclosure, the median crystallite size of the lA-enhanced / 72-LIAH composition is between about 10 nm and about 70 nm. In an embodiment of the present disclosure, the median crystallite size of the lA-enhancedH2-L\ AH composition is between about 25 nm and about 40 nm. Those skilled in the art, having benefited from the teaching of the present disclosure, will understand how to tailor manufacturing conditions to provide lA-enhanced / 72-LIAH compositions within the noted ranges. For example, the following parameters may be controlled to induce smaller crystallite size:• increasing the dilution of the reaction mixture in step (i), and / or step (ii), and / or step (v);• increasing the reaction mixture temperature in step (i);• minimizing crystallization time during step (i) and / or step (iiv);• introducing filtration prior to step (ii), and / or step (iii); and• introducing particulate size control (e.g., sieving or filtering).

[0171] In an embodiment of the present disclosure, the median crystallite size of the lA-enhanced / 72-LIAH composition is determined by scanning electron microscopy (SEM).

[0172] In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition may have an aluminum : lithium molar ratio of at least about 1.9 : 1.0. In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition may have an aluminum : lithium molar ratio of between about 2.0 : 1.0 and about 3.0 : 1.0. In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition may have an aluminum : lithium molar ratio of between about 2.4 : 1.0 and about 2.6 : 1.0. Those skilled in the art will appreciate that such elemental ratios may be determined by ICP or another suitable analytical technique.

[0173] In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition may be as described in Formula 1 :LiaX mAI(OH)3 nH2OCr Formula 1 wherein: a is about 1 ;X is a monovalent anion (e.g. F; Cl; Br, and / or I’); m is between about 1.9 and about 3.0; n is between about 2.4 and about 4.3; andH2Ocr specifies crystallization-hydrate.

[0174] In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition may be a lithium-aluminum-layered-double-hydroxide composition.

[0175] In an embodiment of the present disclosure, the sorbent may further comprise a binding agent, an encapsulating agent, or a combination thereof. Suitable agents may be organic or inorganic and may include alginates, biochars, biopolymers, carbonaceous ores, clays, polyvinyl alcohols, methyacrylates, graphenes, metal organic frameworks, nanotubes, polyphenols, synthetic polymers, polysaccharides, silicates, combinations thereof, and the like.

[0176] In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition may have a lithium uptake capacity of at least about 8.0 mg / mL. In an embodiment of the present disclosure, the lithium uptake capacity of the lA-enhanced / 72-LIAH composition may be at least about 9.0 mg / mL. In an embodiment of the present disclosure, the lithium uptake capacity of the lA-enhanced / 72-LIAH composition may be between about 9.5 mg / mL and about 12.0 mg / mL. Those skilled in the art, having benefited from the teaching of the present disclosure, will understand how to tailor manufacturing conditions to provide lA-enhanced / 72-LIAH composition within the noted ranges. For example, the following parameters may be controlled to induce larger particle sizes (reference numerals related to the method of manufacturing steps described herein):• increasing the concentration of the hydroxide solution used in step (i) and / or step (iii), and / or step (v);• increasing the pH of the reaction mixture above about 9.0 (for example to about 10.0 or about 11.0) in step (iii);• reducing the pH of the reaction mixture below about 4.0 (for example to about 3.0 or about 2.0) in step (i);• reducing the reaction time for step (i), and / or step (ii), and / or step (v);• at step (vi), drying the gel-like material at a temperature of between about 85 "C and 120 C;• at step (vi), drying the gel-like material at thickness of at least about 4 cm;• at step (vi), drying the gel-like material for about between about 24 h and about 72 h; and / or• at step (vi), drying the gel-like material to a mass reduction between about 30% and about 60%.

[0177] In an embodiment of the present disclosure, suspending the lA-enhanced / 72-LIAH composition in deionized water may provide a solution having a pH of between about 7.0 and about 6.2. The lA-enhanced / 72-LIAH compositions of the present disclosure may retain relatively low concentrations of residual hydroxide ions. For example, suspending an lA-enhanced / 72-LIAH composition of the present disclosure in deionized water may provide a solution having a pH of less than about 5, less than about 6, or between about 6.5 and about 7. This may be beneficial in that the formation of insoluble hydroxides may result from exposure to complex brines. Without being bound to any particular theory, complex brines may include relatively high concentrations of divalent ions such as Ca2+and Mg2+, which may precipitate out of solutions of solutions containing relatively high concentrations of hydroxides, and this may manifest as an increase in pressure drop within the sorbent column which leads to lower operating flow rates and lower lithium uptake performance. The lA-enhanced / 72-LIAH composition of the present disclosure may attenuate this issue.

[0178] In an embodiment of the present disclosure, suspending the lA-enhanced / 72-LIAH composition in deionized water may provide a turbidity value of less than 60 NTU. In an embodiment of the present disclosure, suspending the lA-enhanced / 72-LIAH composition in deionized water may provide a turbidity value of less than 10 NTU. In an embodiment of the present disclosure, suspending the lA-enhanced / 72-LIAH composition in deionized water may provide a turbidity value of between about 5 NTU and about 10 NTU. This may be beneficial for DLE sorbent process engineering in that it may correlate with improved structural integrity during process flow. In the context of the present disclosure, turbidity measurement may involve suspending a unit of material in deionizedwater and gently mixing to disperse. The suspension may be decanted out into a separate beaker and turbidity measurements may be conducted on the decanted solutions.

[0179] In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition has a hardness value of at least about 30 psi. In an embodiment of the present disclosure, the hardness value of the lA-enhanced / 72-LIAH composition is between about 32 psi and about 80 psi. Without being bound to any particular theory, the high hardness of the / 72-LIAH compositions of the present disclosure may be a physical manifestation of a high degree of crystallinity, a high degree of incorporation of amorphous regions throughout crystallite agglomerates, or a combination thereof, and this hardness may underlie their performance as sorbents for DLE. Sorbent materials are subjected to high pressure, both as a result of column fluid (e.g., brine, eluent) flow and sorbent bed packing. Materials that resist both these and other physical operational stresses improve overall performance.

[0180] In an embodiment of the present disclosure, the hardness value of the lA-enhanced / 72-LIAH composition is determined by bulk crush strength analysis (e.g., ASTM-D7084).

[0181] In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition may be robust with respect to degradation for at least about 500 column cycles. In an embodiment of the present disclosure, the lA-enhanced / 72-LIAH composition is robust with respect to degradation for at least about 5,000 column cycles.

[0182] An aspect of the present disclosure relates to a method of manufacturing an lA-enhanced / 72-LIAH composition, the method comprising:(i) contacting an initial aliquot of a hydroxide solution with a solution comprising a lithium halide and an aluminum halide to form a reaction mixture in which the lithium halide and aluminum halide are in excess such that the pH of the reaction mixture is reduced to less than about 2.0;(ii) adding an additional aliquot of the hydroxide solution to the reaction mixture to increase the pH of the reaction mixture to between about 1.5 and about 5.5;(iii) heating the reaction mixture to at least about 60 °C;(iv) aging the reaction mixture for about at least about 2 hours, after which time the mixture forms a gel-like material; and(v) adding an additional aliquot of the hydroxide solution to the reaction mixture to increase the pH of the reaction mixture to between about 5.5 and about 7.5.

[0183] In an embodiment of the present disclosure, in step (i) the solution comprising the lithium halide and the aluminum halide is added to the initial aliquot of the hydroxide solution.

[0184] In an embodiment of the present disclosure, in step (i) the hydroxide solution has a pH of between about 9.0 and about 13.5.

[0185] In an embodiment of the present disclosure, in step (i) the pH of the reaction mixture is reduced to between about 1.5 and about 4.0.

[0186] In an embodiment of the present disclosure, in step (ii) the gel-like material has a gel strength of at least about 125 Pa.

[0187] In an embodiment of the present disclosure, in step (ii) the gel strength of the gel-like material is between about 125 Pa and about 400 Pa.

[0188] In an embodiment of the present disclosure, in step (ii) the gel strength of the gel-like material is between about 150 Pa and about 250 Pa.

[0189] In an embodiment of the present disclosure, in step (ii) the viscosity of the reaction mixture is between about 20,000 mPa*s and about 35,000 mPa*s.

[0190] In an embodiment of the present disclosure, in step (ii) the gel strength of the gel-like material and the viscosity of the reaction mixture are determined by rheometric analysis.

[0191] In an embodiment of the present disclosure, in step (iv) the reaction mixture is heated to at least about 60 °C.

[0192] In an embodiment of the present disclosure, in step (iv) the reaction mixture is heated to between about 65 °C and about 95 °C.

[0193] In an embodiment of the present disclosure, the initial aliquot of the hydroxide solution and the additional aliquot of the hydroxide solution are derived from the same stock solution.

[0194] In an embodiment of the present disclosure, the solution comprising the lithium halide and the aluminum halide has a lithium : aluminum molar ratio of between about 1.0 : 2.0 and about 1.0 : 3.0.

[0195] In an embodiment of the present disclosure, the hydroxide solution has a concentration of between about 15.0 w / w% and about 22.0 w / w%.

[0196] In an embodiment of the present disclosure, the lithium halide is lithium fluoride, lithium chloride, lithium bromide, lithium iodide, or a combination thereof.

[0197] In an embodiment of the present disclosure, the lithium halide is lithium chloride.

[0198] In an embodiment of the present disclosure, the aluminum halide is aluminum trifluoride, aluminum trichloride, aluminum tribromide, aluminum triiodide, or a combination thereof.

[0199] In an embodiment of the present disclosure, the aluminum halide is aluminum trichloride.

[0200] In an embodiment of the present disclosure, the hydroxide solution is a sodium hydroxide solution, a potassium hydroxide solution, a calcium hydroxide solution, a magnesium hydroxide solution, or a combination thereof.

[0201] In an embodiment of the present disclosure, the hydroxide solution is a sodium hydroxide solution.

[0202] In an embodiment of the present disclosure, in step (i), step (ii), step (iii), step (iv), step (v), or a combination thereof, the reaction mixture is agitated to modulate the viscosity of the reaction mixture.

[0203] In an embodiment of the present disclosure, in step (i), step (ii), step (iii), step (iv), step (v), or a combination thereof, the temperature of the reaction mixture is controlled to modulate the viscosity of the reaction mixture.

[0204] In an embodiment of the present disclosure, in step (i), step (ii), step (iii), step (iv), step (v), or a combination thereof, the pressure of the reaction mixture is controlled to modulate the viscosity of the reaction mixture.

[0205] In an embodiment of the present disclosure, in step (i), step (ii), step (iii), step (iv), step (v), or a combination thereof, the reaction time is controlled to modulate the viscosity of the reaction mixture.

[0206] In an embodiment of the present disclosure, the method further comprises: (vi) finishing the lA-enhanced H2-LIAH composition by curing, aging, rinsing, desalting, drying, milling, and / or sieving the reaction mixture.

[0207] In an embodiment of the present disclosure, step (vi) comprises curing the reaction mixture for at least about 15 minutes.

[0208] In an embodiment of the present disclosure, in step (vi) the reaction mixture is cured for between about 15 minutes and about 20 hours.

[0209] In an embodiment of the present disclosure, step (vi) comprises desalting the reaction mixture by rinsing, washing, decanting, centrifuging, filtrating, or a combination thereof.

[0210] In an embodiment of the present disclosure, step (vi) comprises desalting the reaction mixture by decanting.

[0211] In an embodiment of the present disclosure, step (vi) comprises drying the reaction mixture at or below about 760 mmHg.

[0212] In an embodiment of the present disclosure, step (vi) comprises drying the reaction mixture at a pressure between about 76 mmHg and 760 mmHg.

[0213] In an embodiment of the present disclosure, step (vi) comprises drying the reaction mixture at a temperature of at least about 70 °C.

[0214] In an embodiment of the present disclosure, step (vi) comprises drying the reaction mixture at a temperature between about 80 °C and about 135 °C.

[0215] In an embodiment of the present disclosure, step (vi) comprises drying reaction mixture at a temperature between about 90 °C and about 120 °C.

[0216] In an embodiment of the present disclosure, step (vi) comprises drying reaction mixture for between about 30 minutes and about 75 hours. In an embodiment of the present disclosure, in step (i), the lithium halide and the aluminum halide is added to an initial aliquot of the hydroxide solution.

[0217] An aspect of the present disclosure relates to a sorbent manufactured by a method as described herein.

[0218] An aspect of the present disclosure relates to an apparatus for recovering lithium from a lithium containing solution, the apparatus comprising: a container having an inlet, an outlet, and a contiguous flow path therebetween; and a sorbent comprising an lA-enhanced / 72-LIAH composition having: (i) a crystallization-hydrate : lithium molar ratio of at least about 2.1 : 1.0; (ii) an amorphous aluminate content of at least about 20%; and (iii) a median crystallite size of less than about 70 nm.

[0219] An aspect of the present disclosure relates to an apparatus for recovering lithium from a lithium containing solution, the apparatus comprising: a container having an inlet, an outlet, and a contiguous flow path therebetween; and a sorbent as defined herein.

[0220] An aspect of the present disclosure relates to a method for recovering lithium from a lithium containing solution, the method comprising: contacting the lithium containing solution with a sorbent composition to extract lithium from the lithium containing solution; and eluting lithium from the sorbent composition to form a lithium eluate solution,wherein the sorbent composition comprises an lA-enhanced / 72-LIAH composition having: (i) a crystallization-hydrate : lithium molar ratio of at least about 2.1 : 1.0; (ii) an amorphous aluminate content of at least about 20%; and (iii) a median crystallite size of less than about 70 nm.

[0221] An aspect of the present disclosure relates to a method for recovering lithium from a lithium containing solution, the method comprising: contacting the lithium containing solution with a sorbent composition to extract lithium from the lithium containing solution; and eluting lithium from the sorbent composition to form a lithium eluate solution, wherein the sorbent composition comprises an lA-enhanced / 72-LIAH composition having: (i) a crystallization-hydrate : lithium molar ratio of at least about 2.1 : 1.0; (ii) an amorphous aluminate content of at least about 20%; and (iii) a median crystallite size of less than about 70 nm.

[0222] An aspect of the present disclosure relates to a method for recovering lithium from a lithium containing solution, the method comprising: contacting the lithium containing solution with a sorbent comprising an lA-enhanced / 72-LIAH composition to extract lithium from the lithium containing solution; and eluting lithium from the sorbent to form a lithium eluate solution, wherein the lA-enhanced / 72-LIAH composition has: (i) a crystallization-hydrate : lithium molar ratio of at least about 2.1 : 1.0; (ii) an amorphous aluminate content of at least about 20%; and (iii) a median crystallite size of less than about 70 nm.Further remarks

[0223] Although the present invention has been described and illustrated with respect to preferred embodiments and preferred uses thereof, it is not to be so limited since modifications and changes can be made therein which are within the full, intended scope of the invention as understood by those skilled in the art.

[0224] While particular aspects of the subject matter described herein have been shown and described, it will be apparent to those skilled in the art that, based upon the teachings herein, changes and modifications may be made without departing from the subject matter described herein and its broader aspects and, therefore, the appendedclaims are to encompass within their scope all such changes and modifications as are within the true spirit and scope of the subject matter described herein.

[0225] Note that the same features of the present invention may be represented by more than one numeral in the specification and drawings. For example, a feature denoted by numeral 100 in Figure 1 , may be denoted by 200 in Figure 2, may be denoted by 300 in Figure 3, etc. Features denoted with the same numeral in different figures are the equivalent and / or same feature but in different embodiments and should be considered equivalent and / or the same for the purposes of interpreting the specification and / or drawings.

[0226] It will be understood by those skilled in the art that, in general, terms used herein, and especially in the appended claims are generally intended as "open" terms (e.g., the term "comprising" should be interpreted as "including but not limited to”," the term "having" should be interpreted as "having at least," the term "has" should be interpreted as "has at least," etc.).

[0227] It will be further understood by those skilled in the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases "at least one" and "one or more" to introduce claim recitations. However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles "a" or "an" limits any particular claim containing such introduced claim recitation to claims containing only one such recitation, even when the same claim includes the introductory phrases "one or more "or "at least one" and indefinite articles such as "a" or "an" (e.g., "a" and / or "an" should typically be interpreted to mean "at least one" or "one or more"); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should typically be interpreted to mean at least the recited number (e.g., the bare recitation of "two recitations," without other modifiers, typically means at least two recitations, or two or more recitations).

[0228] Furthermore, in those instances where a convention analogous to "at least one of A, B, and C, etc" is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., "a system having at least one of A, B, and C" would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). In those instances where a convention analogous to "at least one of A, B, or C, etc." is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., "a system having at least one of A, B, or C" would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.).

[0229] It will be further understood by those skilled in the art that typically a disjunctive word and / or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms unless context dictates otherwise. For example, the phrase "A or B" will be typically understood to include the possibilities of "A" or "B" or "A and B."

[0230] With respect to the appended claims, those skilled in the art will appreciate that recited operations therein may generally be performed in any order. Also, although various operational flows are presented in a sequence(s), it should be understood that the various operations may be performed in other orders than those which are illustrated, or may be performed concurrently. Examples of such alternate orderings may include overlapping, interleaved, interrupted, reordered, incremental, preparatory, supplemental, simultaneous, reverse, or other variant orderings, unless context dictates otherwise.

[0231] Throughout this application, the terms "in an embodiment", "in one embodiment", "in an embodiment", "in several embodiments", "in at least one embodiment", "in various embodiments," and the like, may be used. Each of these terms, and all such similar terms should be construed as "in at least one embodiment, and possibly but not necessarily all embodiments," unless explicitly stated otherwise. Specifically, unless explicitly stated otherwise, the intent of phrases like these is to provide non-exclusive and non-limiting examples of implementations of the subject matter.

[0232] The term of degree “substantially”, as used herein means a reasonable amount of deviation of the modified term such that the end result is not significantly changed. The term “substantially” should be construed as including a deviation of ±5% of the modified term if this deviation would not negate the meaning of the term it modifies. The terms of degree “about” and “approximately should be construed as including a deviation of ±20%. For example, when the terms “approximately” or “about” are used in relation to a numerical value, they modify it above and below by a 20% variation compared to the nominal value. This term can also take into account, for example, the experimental error of a measuring device or rounding. Other terms of degrees should be construed as including a deviation of ±5% of the modified term.

[0233] When a range of values is mentioned herein, the lower and upper limits of the range are, unless otherwise indicated, always included in the definition. When a range of values is mentioned herein, then all intermediate ranges and subranges, as well as individual values included in the ranges, are intended to be included.

[0234] The mere statement that one, some, or may embodiments include one or more things or have one or more features, does not imply that all embodiments include one or more things or have one or more features, but also does not imply that such embodiments must exist. It is a mere indicator of an example and should not be interpreted otherwise, unless explicitly stated as such.

[0235] Those skilled in the art will appreciate that the foregoing specific exemplary compositions, apparatus, and / or methods are representative of more general processes and / or devices and / or technologies taught elsewhere herein, such as in the appended claims filed and / or elsewhere in the present disclosure.

Claims

CLAIMS1. A sorbent for recovering lithium from a lithium containing solution, the sorbent comprising an intrinsic-amorphicity enhanced high-hydration lithium incorporated aluminum hydroxide (JA-enhanced / 72-LIAH) composition having: a crystallization-hydrate : lithium molar ratio of at least about 2.1 : 1.0; an amorphous aluminate content of at least about 20%; and a median crystallite size of less than about 70 nm.

2. The sorbent of claim 1 , wherein the median crystallite size of the lA-enhanced / 72-LIAH composition is between about 0.5 nm and about 70 nm.

3. The sorbent of claim 1 or 2, wherein the median crystallite size of the IA- enhanced / 72-LIAH composition is between about 5 nm and about 20 nm.

4. The sorbent of any one of claims 1 to 3, wherein the median crystallite size of the lA-enhanced / 72-LIAH composition is determined by scanning electron microscopy (SEM).

5. The sorbent of any one of claims 1 to 4, wherein the amorphous aluminate content of the lA-enhanced / 72-LIAH composition is between about 20% and about 50%.

6. The sorbent of any one of claims 1 to 5, wherein the amorphous aluminate content of the lA-enhanced / 72-LIAH composition is between about 23% and about 35%.

7. The sorbent of any one of claims 1 to 6, wherein the amorphous aluminate content of the lA-enhanced / 72-LIAH composition is between about 26% and about 31%.

8. The sorbent of any one of claims 1 to 7, wherein the amorphous aluminate content of the lA-enhanced / 72-LIAH composition is determined by X-ray diffraction (XRD).

9. The sorbent of any one of claims 1 to 8, wherein the crystallization-hydrate : lithium molar ratio of the lA-enhanced / 72-LIAH composition is between about 2.1 : 1.0 and about 4.3 : 1.0.

10. The sorbent of any one of claims 1 to 9, wherein the crystallization-hydrate : lithium molar ratio of the lA-enhanced / 72-LIAH composition is between about 2.4 : 1.0 and about 4.0 : 1.0.

11. The sorbent of any one of claims 1 to 10, wherein the crystallization-hydrate : lithium molar ratio of the lA-enhanced / 72-LIAH composition is between about 2.7 : 1.0 and about 3.5 : 1.0.

12. The sorbent of any one of claims 1 to 11, wherein the crystallization-hydrate : lithium molar ratio of the lA-enhanced / 72-LIAH composition is determined from differential scanning calorimetry (DSC), inductively-coupled plasma optical emission spectroscopy (ICP-OES), thermogravimetric analysis (TGA), or a combination thereof.

13. The sorbent of any one of claims 1 to 12, wherein the lA-enhanced / 72-LIAH composition has an X-ray diffraction (XRD) pattern having 20 reflectance peaks at approximately 11.5 °20, 20.1 °20, 23.1 °20, 35.0 °20, 35.7 °20, or a combination thereof.

14. The sorbent of any one of claims 1 to 13, wherein the lA-enhanced / 72-LIAH composition has an XRD pattern having an absence of 20 reflectance peaks at 18.2 °20.

15. The sorbent of any one of claims 1 to 14, wherein the lA-enhanced / 72-LIAH composition has an aluminum : lithium molar ratio of at least about 1.9 : 1.0.

16. The sorbent of claim 15, wherein the aluminum : lithium molar ratio of the lA-enhanced / 72-LIAH composition is between about 2.0 : 1.0 and about 3.5 : 1.0.

17. The sorbent of claim 15, wherein the aluminum : lithium molar ratio of the lA-enhanced / 72-LIAH composition is between about 2.4 : 1.0 and about 3.6 : 1.0.

18. The sorbent of any one of claims 15 to 17, wherein the aluminum : lithium ratio of the lA-enhanced / 72-LIAH composition is determined from inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis.

19. The sorbent of any one of claims 1 to 18, wherein the lA-enhanced / 72-LIAH composition is as described in Formula 1:LiaX mAI(OH)3 nH2OCr Formula 1 wherein: a is about 1; X is a monovalent anion m Is between about 1.9 and about 3.6; n Is between about 2.1 and about 4.3; and H2Ocr specifies crystallization-hydrate20. The sorbent of claim 19, wherein the monovalent anion X is chloride.

21. The sorbent of any one of claims 1 to 20, wherein the lA-enhanced / 72-LIAH composition is a lithium-aluminum-layered-double-hydroxide composition.

22. The sorbent of any one of claims 1 to 21 , which further comprises a binding agent, an encapsulating agent, or a combination thereof.

23. The sorbent of any one of claims 1 to 22, wherein the lA-enhanced / 72-LIAH composition has a lithium-uptake capacity of at least about 8.0 mg / mL.

24. The sorbent of any one of claims 1 to 23, wherein the lithium-uptake capacity of the lA-enhanced / 72-LIAH composition is at least about 9.0 mg / mL.

25. The sorbent of any one of claims 1 to 24, wherein the lithium-uptake capacity of the lA-enhanced / 72-LIAH composition is between about 9.5 mg / mL and about 12.0 mg / mL.

26. The sorbent of any one of claims 1 to 25, wherein the lA-enhanced / 72-LIAH composition has a hardness value of at least about 30 psi.

27. The sorbent of claim 26, wherein the hardness value of the lA-enhanced / 72-LIAH composition is between about 32 psi and about 80 psi.

28. The sorbent of claim 26 or 27, wherein the hardness value of the lA-enhanced / 72-LIAH composition is determined by bulk crush strength analysis.

29. The sorbent of any one of claims 1 to 28, wherein lA-enhanced / 72-LIAH composition slurry has a particle size distribution (PSD) d50 value of less than 90 pm.

30. The sorbent of claim 29, wherein the slurry PSD d50 value of the lA-enhanced / 72-LIAH composition is between about 10 pm and about 85 pm.31 . The sorbent of claim 29 or 30, wherein the slurry PSD d50 value of the IA- enhanced / 72-LIAH composition is between about 30 pm and about 50 pm.

32. The sorbent of any one of claims 29 to 31 , wherein the slurry PSD d50 value of the lA-enhanced / 72-LIAH composition is determined by laser diffraction particle size analysis.

33. The sorbent of any one of claims 1 to 32, wherein the lA-enhanced / 72-LIAH composition has a Brunauer-Emmett-Teller (BET) surface area of at least about 60 m2 / g.

34. The sorbent of claim 33, wherein the BET surface area of the lA-enhanced H2- LIAH composition is between about 60 m2 / g and about 150 m2 / g.

35. The sorbent of claim 33 or 34, wherein the BET surface area of the lA-enhanced / 72-LIAH composition is between about 75 m2 / g and about 125 m2 / g.

36. The sorbent of any one of claims 1 to 35, wherein the lA-enhanced / 72-LIAH composition has a turbidity value of less than 60 NTU.

37. The sorbent of claim 36, wherein the turbidity value of the lA-enhanced / 72-LIAH composition is between about 5 NTU and about 55 NTU.

38. The sorbent of claim 36 or 37, wherein the turbidity value of the lA-enhanced / 72-LIAH composition is determined with a turbidimeter by suspending the lA-enhanced H2-LIAH composition in deionized water.

39. The sorbent of any one of claims 1 to 38, wherein the lA-enhanced / 72-LIAH composition is physically durable for at least about 2,000 column cycles.

40. A method of manufacturing an intrinsic-amorphicity enhanced high-hydration lithium incorporated aluminum hydroxide (JA-enhanced / 72-LIAH) composition, the method comprising:(i) contacting an initial aliquot of a hydroxide solution with a solution comprising a lithium halide and an aluminum halide to form a reaction mixture in which the lithium halide and aluminum halide are in excess such that the pH of the reaction mixture is reduced to less than about 2.0;(ii) adding an additional aliquot of the hydroxide solution to the reaction mixture to increase the pH of the reaction mixture to between about 1.5 and about 5.5;(iii) heating the reaction mixture to at least about 30 °C;(iv) aging the reaction mixture for about at least about 2 hours, after which time the mixture forms a gel-like material; and(v) adding an additional aliquot of the hydroxide solution to the reaction mixture to increase the pH of the reaction mixture to between about 5.5 and about 7.5.41 . The method of claim 40, wherein in step (i) the solution comprising the lithium halide and the aluminum halide is added to the initial aliquot of the hydroxide solution.

42. The method of claim 40 or 41 , wherein in step (i) the hydroxide solution has a pH of between about 9.0 and about 13.5.

43. The method of any one of claims 40 to 42, wherein in step (i) the pH of the reaction mixture is reduced to between about 1.5 and about 4.0.

44. The method of any one of claims 40 to 43, wherein in step (ii) the reaction mixture is heated to at least about 35 °C.

45. The method of any one of claims 40 to 44, in step (ii) the reaction mixture is heated to between about 35 °C and about 95 °C.

46. The method of any one of claims 40 to 45 wherein in step (iv) the gel-like material has a gel strength of at least about 125 Pa.

47. The method of claim 46, wherein in step (iv) the gel strength of the gel-like material is between about 125 Pa and about 400 Pa.

48. The method of claim 46 or 47, wherein in step (iv) the gel strength of the gel-like material is between about 150 Pa and about 250 Pa.

49. The method of any one of claims 40 to 48, wherein in step (iv) the viscosity of the reaction mixture is between about 20,000 mPa*s and about 35,000 mPa*s.

50. The method of any one of claims 45 to 49, wherein in step (iv) the gel strength of the gel-like material is determined by rheometric analysis. The rheometric analysis was performed at about 3 RPM.

51. The method of any one of claims 40 to 50, the initial aliquot of the hydroxide solution and the additional aliquots of the hydroxide solution are derived from the same stock solution.

52. The method of any one of claims 40 to 51 , wherein the solution comprising the lithium halide and the aluminum halide has a lithium : aluminum molar ratio of between about 1.0 : 2.0 and about 1.0 : 3.0.

53. The method of any one of claims 40 to 52, wherein the hydroxide solution has a concentration of between about 15.0 w / w% and about 50.0 w / w%.

54. The method of any one of claims 40 to 53, wherein the lithium halide is lithium fluoride, lithium chloride, lithium bromide, lithium iodide, or a combination thereof.

55. The method of any one of claims 40 to 54, wherein the lithium halide is lithium chloride.

56. The method of any one of claims 40 to 55, wherein the aluminum halide is aluminum trifluoride, aluminum trichloride, aluminum tribromide, aluminum triiodide, or a combination thereof.

57. The method of any one of claims 40 to 56, wherein the aluminum halide is aluminum trichloride.

58. The method of any one of claims 40 to 57, wherein the hydroxide solution is a sodium hydroxide solution, a potassium hydroxide solution, a calcium hydroxide solution, a magnesium hydroxide solution, or a combination thereof.

59. The method of any one of claims 40 to 58, wherein the hydroxide solution is a sodium hydroxide solution.

60. The method of any one of claims 40 to 59, wherein in step (i), step (ii), step (iii), step (iv), step (v), or a combination thereof, the reaction mixture is agitated to modulate the viscosity of the reaction mixture.

61. The method of any one of claims 40 to 60, in step (i), step (ii), step (iii), step (iv), step (v), or a combination thereof, the temperature of the reaction mixture is controlled to modulate the viscosity of the reaction mixture.

62. The method of any one of claims 40 to 61, wherein in step (i), step (ii), step (iii), step (iv), step (v), or a combination thereof, the pressure of the reaction mixture is controlled to modulate the viscosity of the reaction mixture.

63. The method of any one of claims 40 to 62, wherein in step (i), step (ii), step (iii), step (iv), step (v), or a combination thereof, the reaction time is controlled to modulate the viscosity of the reaction mixture.

64. The method of any one of claims 40 to 63, which further comprises: (vi) finishing the lA-enhanced / 72-LIAH composition by curing, aging, rinsing, desalting, drying, milling, and / or sieving the reaction mixture.

65. The method of claim 64, wherein step (vi) comprises curing the reaction mixture for at least about 15 min.

66. The method of claim 64 or 65, wherein step (vi) the reaction mixture is cured for between about 15 minutes and about 20 hours.

67. The method of any one of claims 64 to 66, wherein step (vi) comprises desalting the reaction mixture by rinsing, washing, decanting, centrifuging, filtrating, or a combination thereof.

68. The method of any one of claims 64 to 67, wherein step (vi) comprises desalting the reaction mixture by decanting.

69. The method of any one of claims 64 to 68, wherein step (vi) comprises drying the reaction mixture at or below about 760 mmHg.

70. The method of any one of claims 64 to 69, wherein step (vi) comprises drying the reaction mixture at a pressure between about 76 mmHg and 760 mmHg.

71. The method of any one of claims 64 to 70, wherein step (vi) comprises drying the reaction mixture at a temperature of at least about 70 °C.

72. The method of any of claims 64 to 71, wherein step (vi) comprises drying the reaction mixture by indirect convective methods, direct convective methods, and / or conductive methods.

73. The method of any one of claims 63 to 72, wherein step (vi) comprises drying the reaction mixture for between about 5 minutes and about 75 hours.

74. An apparatus for recovering lithium from a lithium containing solution, the apparatus comprising: a container having an inlet, an outlet, and a contiguous flow path therebetween; and a sorbent in the container, the sorbent comprising an lA-enhanced / 72-LIAH composition having: (i) a crystallization-hydrate : lithium molar ratio of at least about 2.1 : 1.0, (ii) an amorphous aluminate content of at least about 20%; and (iii) a median crystallite size of less than about 70 nm.

75. An apparatus for recovering lithium from a lithium containing solution, the apparatus comprising: a container having an inlet, an outlet, and a contiguous flow path therebetween; anda sorbent in the container, the sorbent comprising an lA-enhanced / 72-LIAH composition as defined in any one of claims 1 to 39.

76. A method for recovering lithium from a lithium containing solution, the method comprising: contacting the lithium containing solution with a sorbent to extract lithium from the lithium containing solution; and eluting lithium from the sorbent to form a lithium-eluate solution, wherein the sorbent comprises an lA-enhanced / 72-LIAH composition having: (i) a crystal lization-hydrate : lithium molar ratio of at least about 2.1 : 1.0, (ii) an amorphous aluminate content of at least about 20%, and (iii) a median crystallite size of less than about 70 nm.

77. A method for recovering lithium from a lithium containing solution, the method comprising: contacting the lithium containing solution with a sorbent to extract lithium from the lithium containing solution; and eluting lithium from the sorbent to form a lithium-eluate solution, wherein the sorbent comprises an lA-enhanced / 72-LIAH composition as defined in any one of claims 1 to 39.

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