Nanocomposite materials useful for the extraction and recovery of lithium from aqueous solutions

Abstract

The present disclosure relates to nanocomposites that are capable of selectively extracting lithium from lithium-containing liquid sources when the nanocomposites are activated, methods for preparing the nanocomposites, and uses of the nanocomposites for the extraction and recovery of lithium.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the benefits of U.S. Provisional Patent Application No. 63 / 071,790, filed on 28 August 2020. The contents of the aforementioned application are incorporated into this application by reference.

[0002] This disclosure generally relates to nanocomposite materials that enable the selective extraction of lithium from a liquid resource (or liquid source), having opening size limitations (cavities / channels) and nanocrystalline domain size (<100 nm) that allow only the entry and exit of lithium ions contained in the liquid resource while substantially removing all other ions present in the liquid resource; methods for manufacturing nanocomposite materials; and methods for using nanocomposite materials to extract lithium from a liquid resource and subsequently recover the extracted lithium during treatment with an acidic solution. [Background technology]

[0003] The demand for lithium is increasing due to its use in a variety of applications, including lithium-ion batteries (LiBs), which contain Li2CO3, LiOH, metallic Li, LiPF6, LiCl, Li alloys, LiCoO2, and other Li electrode compositions. Specialized glass and ceramics are also significant sources of demand for lithium, such as LiAlSi2O6 (spodumene) and Li2CO3.

[0004] Conventional methods for lithium extraction are based on the improvement of lithium-rich natural minerals such as spodumene and pegmatite by heat treatment and acid treatment. However, since the minerals have to be pulverized, calcined at a high temperature (about 1000 ° C), and treated with sulfuric acid (at 250 ° C) to recover lithium as Li2SO4, these treatments are very costly, energy-intensive, and produce large amounts of waste and undesirable products. Another conventional method for lithium recovery is by natural evaporation of brine in large ponds, usually called "salares". In this particular method, it is highly dependent on the climate, which affects the evaporation rate and thus the concentration of lithium in the brine. A long residence time of 1 to 3 years is required to obtain a suitable brine with a high lithium content (about 6%), and a fairly large area has to be used to create salar ponds, thereby affecting the environment. It has been found that the recoverable estimated amount of lithium by the above conventional methods is about 14,000,000 tons.

[0005] A larger source of lithium can be found in seawater, which has a recoverable estimated amount of 230,000,000,000 tons. However, the concentration of lithium in seawater is very low (0.1 - 0.25 ppm) and is thus not suitable for recovery using the above such conventional methods.

[0006] One alternative method for extracting lithium from other aqueous sources (such as brine), where the lithium concentration can be between 30 ppm and 3,000 ppm, is by the use of ion exchange materials. However, brine also contains other cations such as Na + , K + , Rb + , Cs + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , each at higher concentrations and with a higher charge / size ratio (e.g., Mg 2+ and Ca 2+They can exist (against lithium) and are not selective for lithium and capture all other cations, making it difficult to separate lithium using conventional ion exchange materials (e.g., zeolites).

[0007] Therefore, for an ion exchange material to be suitable for lithium extraction from brine, it must be able to selectively extract lithium ions from all other cations present in the brine. In addition to this "size limitation" (i.e., size exclusion of other cations larger than lithium ions), protons (H) + ) must also be considered, as they possess the charge and size required to move or replace lithium from the ion exchange material during regeneration. Therefore, a suitable ion exchange material must be able to allow the following inlets and outlets (or inlets and outlets): (i) only lithium ions when lithium is selectively extracted by contact with brine; and (ii) proton ions when lithium is recovered as a salt of the acid after contact with the acid during regeneration.

[0008] One of the most well-known conventional adsorbents used for lithium extraction / recovery is layered double aluminum chloride lithium (LiCl-2Al(OH)3). This adsorbent material can be prepared and synthesized differently to allow it to possess specific properties that differentiate it from other LiCl-2Al(OH)3 materials. Therefore, it is possible to produce LiCl-2Al(OH)3 composite materials having similar crystal structures but different properties, and thus they are not the same composite material. This is also true for lithium titanate, lithium manganese, and their composite materials. Lithium titanate is a group of materials containing lithium, titanium, and oxygen atoms that do not exhibit single-crystal materials like LiCl-2Al(OH)3. Instead, there are several lithium titanates with different compositions and different crystal structures. Furthermore, several lithium titanates can have the same composition but different crystal structures. Similarly, lithium manganese has been found to have several crystal structures that differ in form from their compositions, rather than having one unique crystal structure.

[0009] Examples illustrating the above adsorbents for the extraction / recovery of lithium from brine in an ion exchange process can be found in Non-Patent Documents 1 and 2. Three more promising adsorbents include the lithium manganese oxide (Li-Mn-O) group, also known as lithium manganate; the lithium titanium oxide (Li-Ti-O) group, also known as lithium titanate; and layered double aluminum chloride lithium (LiCl-2Al(OH)3) or LDH. When the material is treated with acid during material regeneration and lithium recovery, Mn 2+ The most common problem found with Li-Mn-O is the reduction in ion exchange capacity, as ions dissolve and leach, and therefore have very poor repeat stability (single-life sorbent). While the Li-Ti-O group of sorbents is considered attractive for selectively extracting lithium, 142.9 mg Li / g solidOnly 40% to 50% of the theoretical value can be processed, which may be due to particle aggregation resulting from the high-temperature synthesis of these materials, thereby producing large crystals and highly heterogeneous morphology that affect lithium diffusion and recovery. 4+ While the Li-Ti-O structure is considered stable, problems with this structure likely arise when the material is exposed to acidic solutions for regeneration purposes. LDH can be synthesized by intercalating LiCl to gibbsite (α-Al(OH)3) to produce LiCl-2Al(OH)3, and its low manufacturing cost, environmental friendliness, and ease of regeneration make it an attractive candidate for large-scale plant applications. Problems associated with the use of LDH relate to the ability to control the maximum introduction of lithium into the structure, and therefore have unreliable cycle repeatability.

[0010] Further examples describing materials useful for extracting lithium can be found in Patent Documents 1, 2, 3, 4, 5, 6, and 7. Other documents, such as Patent Documents 8 and 9, describe the production of lithium titanate by very complex and cumbersome methods that make them unsuitable for homogeneous and large-scale production. For example, Patent Document 8 describes a composition Li4Ti5O 12 The goal is to produce lithium titanate having (at least 98% by weight). An additional step in the manufacturing process is to disperse the calcined material so that the resulting microcrystals can be separated. Patent document 9 describes TiO2 and Li2TiO3 or TiO2+Li2TiO3+Li4Ti5O 12 The production of titanate mixtures for the manufacture of cathodes in lithium-ion batteries is described. However, both must be sintered at a temperature range of 800°C to 950°C.

[0011] More recently, Patent Document 10 describes several adsorbents identified by theoretical calculations for lithium extraction and recovery. In particular, lithium metal oxide compounds suitable for lithium extraction were predicted using high-density functional theory and specific ion interaction theory. From the Open Database of Quantum Materials (OQMD) of approximately 400,000 compounds, 77 lithium metal oxide compounds were initially selected under the assumption that they are stable or nearly stable in the "lithified" state. Using the above calculations, 14 compounds from these 77 candidates, including the following, were further considered useful for lithium extraction from brine: Li4TiO4, Li7Ti 11 O 24 , LiTiO2, LiAlO2, LiCuO2, Li2SnO3, Li2MnO3, Li2FeO3, Li3VO4, Li2Si3O7, LiFePO4, Li2CuP2O7, Li4Ge5O 12 Li4GeO4 and Li2MnO3. It is well known to those skilled in the art that the preparation of these materials is extremely important, as a single crystalline material can be prepared in several different ways, thereby resulting in different sizes and morphologies that affect their properties, but this document neither describes nor illustrates this. Furthermore, there are no examples of these proposed materials being used for lithium extraction, only descriptions of the crystalline structure of the solids and their absorption of Li / H, as well as calculations performed under conditions that are typically present in brine. In addition, the teachings described in this document have also been published in Non-Patent Document 3.

[0012] Finally, Patent Document 11 describes an integrated system for lithium extraction from brine and its conversion to a valuable lithium product. A lithium sorbent Li4Mn5O coated with ZrO2 is used to prevent or reduce the dissolution of manganese during lithium recovery during material activation or after acid treatment, which is a known drawback of lithium manganate materials. 12All embodiments teach that the use of [[ID=]] is necessary. The integrated process also uses cationic and anionic conductive membranes composed of functionalized polymer structures having a thickness of about 1 μm to about 10 mm, and one or more electrochemical reduction electrodes composed of titanium, niobium, zirconium, tantalum, magnesium, titanium dioxide, their oxides, or combinations thereof.

[0013] Despite the above, there is a continuing need to develop new adsorbent materials that can be used in ion exchange processes to selectively extract lithium from multiple complex brines and then recover it in high yields when contacted with an acid.

Prior Art Documents

Patent Documents

[0014]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Patent Document 9

Patent Document 10

Patent Document 11

[0015] [Non-Patent Document 1] “Lithium recovery from aqueous resources and batteries -a brief review,”Johnson Matthey Technology Review,2018,62(2),161-176 [Non-Patent Document 2] G. Liu, Z. Zhao, A. Ghahreman, “Novel approaches for lithium extraction from salt-lake brines: a review”, Hydrometallurgy, 2019, 187, 81-100 [Non-Patent Document 3] “Computational Discovery of Li-MO Ion Exchange Materials for Lithium Extraction from Brines”;Chem.Mater.2018,30,6961-6968 [Overview of the Initiative] [Means for solving the problem]

[0016] This disclosure relates to a nanomaterial (or nanocomposite material) in which at least one lithium source (or lithium source or lithium source) is mixed in an aqueous medium with at least one other source selected from a silicon source (or silicon source or silicon source), an aluminum source (or aluminum source or aluminum source), a titanium source (or titanium source or titanium source), a zirconium source (or zirconium source or zirconium source), a metal phosphate source (or metal phosphate source or metal phosphate source), and mixtures thereof to form a suspension (or suspension) with an atomic molar ratio (or molar ratio) of at least 2.0:1 of lithium to “other source” and the suspension is subjected to hydrothermal treatment (or hydrothermal treatment) A nanocomposite material is provided, which is obtained by subjecting (or providing) a nanocomposite material to a heat treatment, and by optionally subjecting (or providing) the nanocomposite material to a heat treatment, and which has a domain size (or region size) of less than about 100 nm.

[0017] Accordingly, embodiments within the scope of the present disclosure include the steps of preparing a slurry, for example, adding a lithium source (e.g., a lithium source for lithium hydroxide) to a dispersion in an aqueous medium of another source, such as nanocrystalline oxides like TiO2, ZrO2, or amorphous nanomaterials like colloidal SiO2 and mixtures thereof, and subjecting the slurry to a hot water treatment to produce the nanocomposite materials of the present disclosure. These produced nanocomposite materials can be further subjected to heat treatment (or heat treatment) to control or enhance their stability and performance at temperatures in the range of about 100°C to about 1050°C and for a period of about 1 hour to about 84 hours.

[0018] Nanocomposite materials can be shaped (or molded) or sized for use in a fixed-bed ion-exchange process. For example, the nanocomposite material can be placed (or loaded) into a column, and then activated by contacting the composite material with an acid solution to exchange lithium ions for hydrogen ions. The liquid resource is then passed through the ion-exchange column to selectively extract lithium from the liquid resource, thereby forming a lithium-rich nanocomposite material (or lithium-rich or abundant nanocomposite material, lithium-enriched nanomaterial composite) (i.e., hydrogen ions are exchanged for lithium ions). The lithium-rich nanocomposite material is then contacted with an acid solution to recover lithium as a lithium salt. [Brief explanation of the drawing]

[0019] [Figure 1] This is a schematic diagram of one embodiment of lithium extraction / recovery using the ion exchange method of the present disclosure. [Figure 2] This is a schematic diagram of a method for preparing lithium titanate nanocomposite materials according to the present disclosure using a hydrothermal method (or hydrothermal method). [Figure 3] This is the X-ray diffraction pattern of the obtained crystalline phase of lithium titanate in Example 1 of this disclosure. [Figure 4] This is a scanning electron microscope image of the obtained crystalline phase of lithium titanate in Example 1 of this disclosure. [Figure 5] This is the X-ray diffraction pattern of the obtained crystalline phase of lithium titanate in Example 2 of this disclosure. [Figure 6] This is a scanning electron microscope image of the obtained crystalline phase of lithium titanate in Example 2 of this disclosure. [Figure 7] This is the X-ray diffraction pattern of the obtained crystalline phase of lithium titanate in Example 3 of this disclosure. [Figure 8]This is a scanning electron microscope image of the obtained crystalline phase of lithium titanate in Example 3 of this disclosure. [Figure 9] This is the X-ray diffraction pattern of the obtained crystalline phase of lithium silicate in Example 4 of this disclosure. [Figure 10] This is a scanning electron microscope image of the obtained crystalline phase of lithium silicate according to Example 4 of this disclosure. [Figure 11] This is the X-ray diffraction pattern of the obtained crystalline phase of lithium silicate according to Example 5 of this disclosure. [Figure 12] This is a scanning electron microscope image of the obtained crystalline phase of lithium silicate in Example 5 of this disclosure. [Figure 13] This is the X-ray diffraction pattern of the obtained crystalline phase of lithium zirconate in Example 6 of this disclosure. [Figure 14] This is the X-ray diffraction pattern of the obtained crystalline phase of aluminum-doped lithium silicate (or aluminum-doped lithium silicate) according to Example 7 of this disclosure. [Figure 15] This is the X-ray diffraction pattern of the obtained crystalline phase of lithium aluminosilicate in Example 8 of this disclosure. [Figure 16] This is the X-ray diffraction pattern of the obtained crystalline phase of lithium titanate in Example 11 of this disclosure. [Figure 17] This is the X-ray diffraction pattern of the obtained crystalline phase of lithium titanate from Example 11 after calcination at 550°C according to the present disclosure. [Figure 18] The infrared spectra of the crystalline phase of lithium titanate from Example 11, calcined at 550°C, before and after the activation process according to this disclosure are shown. [Figure 19] This is the X-ray diffraction pattern of the lithium nitrate obtained in Example 13 according to this disclosure. [Figure 20] This is a DSC-TGA thermogram of the lithium nitrate salt obtained in Example 13 of this disclosure. [Modes for carrying out the invention]

[0020] This disclosure generally relates to nanocomposite materials prepared for use in processes for selectively extracting lithium from liquid resources and subsequently recovering such lithium, and more particularly to such nanocomposite materials having an affinity for selectively extracting lithium from liquid resources while substantially removing other ions present in the liquid resources. The applicant has found that, when the nanocomposite materials of this disclosure are manufactured according to a particular method, the nanocomposite materials have opening size limitations of their structural openings or window inlets that simply allow lithium ions (and proton ions) to enter and exit the nanocomposite material, and small crystalline domain sizes (or crystalline region sizes, crystallized region sizes, crystalline region sizes, or crystalline domain sizes) in the nanorange (< about 100 nm) that allow for rapid exchange.

[0021] Accordingly, the selected nanocomposite materials of this disclosure are materials prepared to have lithium in their structure, which allows lithium ions to be ion-exchanged with hydrogen ions (i.e., allows lithium to move) upon contact with an acidic solution. In a preferred embodiment, the nanocomposite materials can be produced by a hydrothermal treatment method. Alternative methods such as precipitation methods, solid-phase reaction methods, and combinations thereof with hydrothermal treatment are also within the scope of this disclosure. In these methods, the nanocomposite materials can be prepared by mixing soluble inorganic and organic components in a method that produces a solution, slurry, or gel that can be dried to recover the solid content or subjected to a solid-phase reaction at a temperature in the range of about 100°C to about 1050°C and for a time in the range of about 1 hour to about 84 hours. Alternatively, a pre-prepared solution, slurry, or gel may be directly subjected to a hydrothermal treatment at a temperature in the range of about 60°C to about 250°C and for a time in the range of about 1 hour to about 84 hours. Furthermore, for the purpose of enhancing the structural stability and / or performance of lithium extraction / recovery, a solid produced by a hot water method may be subjected to (or treated with) heat treatment at a temperature in the range of approximately 100°C to approximately 1050°C and for a time in the range of approximately 1 hour to approximately 84 hours.

[0022] Furthermore, this disclosure also provides a method (or process) for recovering lithium extracted from a nanocomposite material by contacting the nanocomposite material with an acidic solution to form a lithium salt.

[0023] The following terms shall have the following meanings:

[0024] The term “comprising” and its derivatives are not intended to exclude the presence of any additional components, processes, or procedures, whether or not they are disclosed herein. To avoid any ambiguity, all compositions claimed herein by the use of the term “comprising” may contain any additional additives or compounds unless otherwise specified. In contrast, where described herein, the term “consisting essentially of” excludes any other components, processes, or procedures from any subsequent enumeration, except those not essential to the usability, and where used, the term “consisting of” excludes any components, processes, or procedures not specifically described or enumerated. The term “or” means the enumerated elements individually and in any combination, unless otherwise specified.

[0025] The articles “a” and “an” are used herein to mean one or more (i.e., at least one) grammatical objects of the article. The phrases “in one embodiment” and “according to one embodiment” generally mean that the particular feature, structure, or characteristic following the phrase is included in at least one embodiment of the Disclosure and may be included in two or more embodiments of the Disclosure. Importantly, such phrases do not necessarily refer to the same embodiment. Where the specification states that a particular component or feature is included or has characteristics, it is not required that that component or feature be included or have characteristics.

[0026] As used herein, the term “about” allows for some degree of variability in the value or range, for example, it may be within 10%, 5%, or 1% of the stated limit of the stated value or range.

[0027] Values ​​expressed in range format should be interpreted flexibly to include not only the numerical limits explicitly stated as the range boundaries, but also all individual numerical values ​​or subranges contained within that range, as if each numerical value and subrange were explicitly stated. For example, a range such as 1 to 6 should be considered to have specifically disclosed subranges such as 1 to 3, 2 to 4, 3 to 6, and the individual numerical values ​​within those ranges, such as 1, 2, 3, 4, 5, and 6. This applies regardless of the size of the range.

[0028] The terms “preferred” and “preferred” refer to embodiments that, under certain circumstances, may provide certain advantages. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the enumeration of one or more preferred embodiments does not imply that other embodiments are unhelpful, nor is it intended to exclude other embodiments from the scope of this disclosure.

[0029] The term "substantially" means the complete or nearly complete degree or extent of an effect, characteristic, nature, state, structure, item, or result.

[0030] The term “substantially absent” means a composition in which a particular compound or part is present in an amount that does not significantly affect the composition. In some embodiments, “substantially absent” may mean a composition in which a particular compound or part is present in an amount of less than 2% by weight, or less than 1% by weight, or less than 0.5% by weight, or less than 0.1% by weight, or less than 0.05% by weight, or even less than 0.01% by weight, based on the total weight of the composition.

[0031] The term "liquid resources" means natural brine, dissolved salt flat, seawater, concentrated seawater, desalination effluents from seawater, concentrated brine, processed brine, oilfield brine, liquids from ion exchange processes, liquids from solvent extraction processes, synthetic brine, leachates from ores or combinations of ores, leachates from minerals or combinations of minerals, leachates from clay or combinations of clays, leachates from recycled products, leachates from recycled materials, effluents from plants for manufacturing cathodes or combinations thereof.

[0032] The term "selectively extracting" or "selective extraction" means removing lithium present in a liquid resource while leaving the rest of the liquid resource unaffected (i.e., substantially all other ions in the liquid resource remain in the liquid resource).

[0033] The terms "optional" or "optionally" mean that the event or situation described thereafter may or may not occur, and that the description includes both cases in which such event or situation occurs and cases in which it does not.

[0034] The nanocomposite materials according to this disclosure can be obtained by the steps of: mixing at least one other source selected from a silicon source, an aluminum source, a titanium source, a zirconium source, a metal phosphate source (or a metal-phosphate source or a metal-phosphate source) and mixtures thereof in an aqueous medium containing at least one lithium source to form a suspension of lithium to the other source (i.e., silicon or aluminum or titanium or zirconium or metal phosphate) in an atomic molar ratio of at least 2.0:1 (or forming a suspension in such an atomic molar ratio); subjecting (or immersing) the suspension in hot water at a temperature of about 60°C to about 250°C for a period of time of about 1 hour to about 84 hours to form a nanocomposite material; and optionally subjecting (or immersing) the nanocomposite material in heat treatment at a temperature between about 100°C and about 1050°C for a period of time of about 1 hour to about 84 hours, wherein the nanocomposite material has a domain size of less than about 100 nm. In some embodiments, the nanocomposite material has a domain size of less than about 90 nm, or less than about 80 nm, or less than about 70 nm, or less than about 60 nm, or less than about 50 nm, or even less than about 40 nm. In other embodiments, the nanocomposite material has a domain size between about 10 nm and about 90 nm, or between about 20 nm and about 60 nm, or between about 30 nm and about 50 nm.

[0035] To enhance the stability and / or performance of the nanocomposite material, other elements may be added to the composite material during its preparation, including, but not limited to, doping elements such as Al, Ti, Zr, Si, Fe, Mn, Zn, Co, Cu, P, or mixtures thereof.

[0036] According to one embodiment, at least one lithium source may be any compound comprising elemental lithium that can release this elemental lithium in a reactive form in an aqueous medium. The lithium source may be selected from lithium salts, preferably lithium chloride, lithium hydroxide, lithium nitrate, lithium sulfate, lithium carbonate, and mixtures thereof.

[0037] According to another embodiment, at least one other source to be mixed with the lithium source includes titanium dioxide, zirconium oxide, silicon dioxide, aluminum nitrate, sodium silicate, aluminum hydroxide, sodium silicate, iron phosphate, zinc phosphate, zinc phosphate, manganese phosphate, or magnesium phosphate.

[0038] Therefore, at least one lithium source and at least one other source selected from silicon, aluminum, titanium, zirconium, and metal phosphate sources are mixed in the presence of water to obtain a suspension. In an alternative embodiment, at least one other source can be treated with an acid or base to produce a precursor to generate (or produce) a suitable homogeneous precipitate or smooth gel (or smoothing gel) that can be washed and dried, and this precursor is then mixed with the lithium source and water. The resulting suspension can then be subjected to a hot water treatment to produce a nanocomposite material. According to the embodiment, the resulting suspension is subjected to a hot water treatment process at a temperature between about 60°C and about 250°C for a period of time between about 1 hour and about 84 hours. Preferably, the hot water treatment is carried out at a temperature between approximately 70°C and approximately 200°C, or between approximately 70°C and approximately 180°C, or between approximately 80°C and approximately 150°C, and for a period of time consisting of approximately 5 hours to approximately 72 hours or approximately 10 hours to approximately 36 hours.

[0039] The above-described hot water treatment process is advantageously carried out according to techniques known to those skilled in the art. According to one embodiment, the hot water treatment is carried out in a reactor (or reactor) under autogenous pressure and in a water-saturated atmosphere. Preferably, the hot water treatment is carried out by introducing a lithium source, water, and other sources (alone or mixed with an acid or base) into the reactor simultaneously or individually. When the other source is introduced into the reactor as a mixture with an acid, the acid is advantageously selected from nitric acid, hydrochloric acid, sulfuric acid, and carboxylic acid. When the other source is introduced into the reactor as a mixture with a base, the base is advantageously selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, and ammonia.

[0040] Preferably, the hot water treatment is carried out in the presence of a humid atmosphere having a water content between about 20% and 100% by weight, preferably between about 50% and 100% by weight, and preferably between 80% and 100% by weight.

[0041] Alternatively, the hot water treatment may be carried out in a weathered furnace in the presence of a moist air flow (or moist air flow) containing water between about 20% and 100% by weight, preferably between about 50% and 100% by weight, or preferably between about 80% and 100% by weight, according to methods known to those skilled in the art, or in a furnace operated under a moist air flow containing water between about 20% and 100% by weight, preferably between about 50% and 100% by weight, or preferably between about 80% and 100% by weight.

[0042] A hydrothermal treatment process carried out under a controlled atmosphere offers (or provides) the possibility of obtaining a crystallized solid material having domain sizes of less than 100 nm or less than 90 nm, less than 80 nm or less than 70 nm, less than 60 nm or less than 50 nm, or less than 40 nm, which has sufficient strength and sufficient mechanical resistance when placed in contact with a liquid resource, acid solution, or water. At the end of the hydrothermal treatment, the obtained nanocomposite material can then be advantageously recovered, optionally washed, and dried. In another embodiment, the obtained nanocomposite material can be subjected to heat treatment as described above.

[0043] Selected nanocomposite materials can be produced by hydrothermal treatment and optionally by heat treatment, but alternative methods such as precipitation methods, solid-phase reaction methods, and combinations thereof with hydrothermal treatment are also within the scope of this disclosure. In these alternative methods, to prepare the nanocomposite material, the above-mentioned soluble inorganic components are mixed to produce a solution, slurry, or gel that can be dried, and the solid is recovered or subjected to a solid-phase reaction at a temperature in the range of about 100°C to about 1050°C and for a time in the range of about 1 hour to 84 hours. Alternatively, a pre-prepared solution, slurry, or gel can be subjected to hydrothermal treatment at the above-mentioned temperature and time (i.e., in the range of about 60°C to about 250°C and for a time in the range of about 1 hour to about 84 hours). The solid produced from the hydrothermal treatment can then be subjected to heat treatment at the above-mentioned temperature and time (i.e., in the range of about 100°C to about 1050°C and for a time in the range of about 1 hour to about 84 hours) to enhance its structural stability and / or performance for lithium extraction / recovery from liquid resources.

[0044] In another embodiment, a colloidal silica solution (or colloidal silica solution) can be mixed with a lithium hydroxide solution (or other lithium salt) to precipitate a solid material for the production of the nanocomposite material of the Disclosure, which can then be washed, dried, and subsequently subjected to hot water treatment at a temperature of about 100°C to about 1050°C for a period of about 1 hour to about 84 hours. In another embodiment, a colloidal silica solution (or other lithium salt) can be mixed with lithium hydroxide (or other lithium salt) to produce the nanocomposite material of the Disclosure, which can then be placed in a reactor as a smooth gel (or smooth or smooth-surfaced gel) and subjected to hot water treatment at a temperature of about 60°C to about 250°C for a period of about 1 hour to about 84 hours. The produced nanocomposite material can be subjected to further heat treatment at a temperature of about 100°C to about 1050°C for a period of about 1 hour to about 84 hours to enhance its stability and performance.

[0045] It is also within the scope of this disclosure to enhance the stability and / or performance of composite materials by adding (or adding) other elements to the composite material, such as elements like Al, Ti, Zr, Si, Fe, Mn, Zn, Co, Cu, P, or mixtures thereof. These elements can further enhance the performance of nanocomposite materials by adding new lithium-supported sites that increase ion exchange with proton ions during the acid treatment process, and thus further increase the recovery of lithium as a lithium salt.

[0046] For example, in one embodiment, a colloidal silica solution can be mixed with lithium hydroxide (or other lithium salts) and an aluminum salt such as Al(NO3)3 or Al(OH)3 to form a smooth doped-aluminum gel which is then placed in a reactor and treated under hot water conditions at temperatures ranging from about 60°C to about 250°C for about 1 to 84 hours to produce an Al-doped lithium silicate (or lithium Al-doped silicate). This can then be subjected to further heat treatment at temperatures ranging from about 100°C to about 1050°C for about 1 to 84 hours to produce an Al-doped lithium silicate nanocomposite material with enhanced stability and performance.

[0047] In another embodiment, to prepare a lithium metal phosphate nanocomposite material, Fe 2+ Zn 2+ Co 2+ Cu 2+ Mn 2+ Ni 2+A transition metal salt having a valence of 2+, such as a 2+ transition metal salt, and mixtures thereof, can be added to an acidic solution of phosphoric acid. The mixture is then reacted with lithium hydroxide (or other lithium salts) to produce a precipitate or smooth gel, which is then washed, dried, and treated with hot water to produce the lithium metal phosphate nanocomposite material of the present disclosure. In another embodiment, an aqueous solution of the mixture containing the above precipitate or smooth gel can be placed in a reactor and treated under hot water conditions at a temperature of about 65°C to about 200°C for a period of about 1 hour to about 84 hours to produce a lithium metal phosphate, which can then be optionally subjected to further heat treatment at a temperature of about 100°C to about 1050°C for a period of about 1 hour to about 84 hours to control or enhance its stability and performance.

[0048] In one embodiment, a powdered nanocomposite material is composited (or has been composited) with a known material (e.g., an inorganic or organic binder, an aggregate (or agglomerate)). This allows the nanocomposite material to be shaped and sized for placement in a fixed-bed ion exchange column, and then activated by contact with an acid solution to form a nanocomposite material containing hydrogen ions.

[0049] Accordingly, in another embodiment, the Disclosure also includes a method for producing (or generating) a lithium salt from a liquid resource, generally comprising the steps of: (i) providing (or supplying) a fixed-bed ion-exchange column, wherein the ion-exchange column comprises a nanocomposite material according to the Disclosure containing hydrogen ions (i.e., the nanocomposite material is in contact with an acid solution having a given acid concentration sufficient to remove lithium ions originally present in the nanocomposite material and to replace them with hydrogen ions); (ii) contacting the nanocomposite material in the ion-exchange column with a liquid resource to selectively extract lithium from the liquid resource, thereby producing a lithium-rich nanocomposite material in which hydrogen ions from the nanocomposite material are exchanged only for lithium ions from the liquid resource (or exclusively for lithium ions); and (c) contacting the lithium-rich nanocomposite material with an acid solution, thereby producing a concentrated lithium salt aqueous solution in which lithium ions from the lithium-rich nanocomposite material are exchanged for hydrogen ions from the acid solution. In particular, the lithium ions exchanged for hydrogen ions form a water-soluble salt containing anions of the respective acids used. For example, if the acid solution contains HCl, LiCl is recovered; if the acid solution contains HNO3, LiNO3 is recovered; if the acid solution contains H2SO4, Li2SO4 is recovered; and if the acid solution contains CH3COOH, Li(CH3COO) is recovered.

[0050] In one embodiment, to first activate a fixed-bed ion exchange column containing a bed of nanocomposite material having a desired size and shape, the composite material is brought into contact with an acid solution having a given acid concentration in an amount sufficient to remove lithium ions originally present in the nanocomposite material, thereby causing a "protonation" form of the sized and shaped nanocomposite material containing hydrogen ions. Next, this activated material (or activated material) is brought into contact with a lithium-containing liquid resource, and the lithium ions contained in the liquid resource are selectively extracted from the liquid resource while other ions present in the liquid resource pass through the column. Depending on the activated nanocomposite material and the lithium-containing liquid resource, the conditions required for extraction are generally known to those skilled in the art and include, for example, the flow rate of the liquid resource, the working temperature, the working pressure, and any other necessary parameters for selectively recovering lithium from the liquid resource. Next, the lithium-rich nanocomposite material is brought into contact with the acid solution to exchange lithium ions for hydrogen ions to produce a concentrated aqueous solution of lithium salt. This concentrated aqueous solution then passes through the column and can be further processed in secondary processes and known process techniques to obtain lithium salt crystals, or improved to produce other types of lithium compounds.

[0051] Figure 1 schematically illustrates a process illustrating the extraction / recovery of lithium by ion exchange using the nanocomposite material of this disclosure. During the extraction process, a liquid resource containing lithium ions is supplied to an ion exchange column, where the nanocomposite material (which is a nanocomposite material that has been pre-activated by contacting the composite material with an acid solution to extract lithium ions and introducing hydrogen ions into its structure) and the lithium ions present in the liquid resource are selectively extracted by ion exchange with the hydrogen ions present in the nanocomposite material, as shown on the left side of the inset in Figure 1. Due to the unique properties of the nanocomposite material, other cations present in the liquid resource are prevented from entering the channels / cavities of the nanocomposite material and thus pass through the column unaffected. In this way, a liquid resource from which lithium has been removed (or a liquid resource substantially free of lithium) is obtained at the outlet of the column. According to embodiments, the liquid resource can be passed through the column in either an upward or downward flow manner, depending on the extraction / recovery system implemented, the type of liquid resource, and the nanocomposite material used. In some embodiments, pretreatment of the liquid resource may be required, depending on the type of liquid resource and the source. Examples of such pretreatment include filtration, the addition of various chemicals to alter pH, or to precipitate undesirable materials. In some embodiments, it may be necessary to raise the temperature of the liquid resource, with a maximum temperature increase of about 100°C, although advantageously, the temperature of the liquid resource is between room temperature and about 80°C. The flow of the liquid resource through the column can be from about 0.0001 total volume (BV) / hour to about 100 BV / hour, and the pressure can be from atmospheric pressure to about 200 psig. After selective extraction of lithium ions, an aqueous detergent can be optionally passed through the column to remove any excess liquid resource that may be present on the surface of the column bed.

[0052] Next, to recover the lithium trapped within the nanocomposite, an acid solution is passed through the nanocomposite so that protons (hydrogen ions) enter the channels / cavities of the nanocomposite and exchange ions with lithium ions, as shown on the right side of the inset in Figure 1. The acid solution may consist of HCl, HNO3, H2SO4, or CH3COOH, depending on the desired lithium salt to be recovered. The concentration of the acid solution used may vary (or be altered) depending on the final desired concentration of the salt selected as the target product. The temperature of the acid solution is room temperature (approximately 22°C to approximately 25°C), which is advantageous because stripping is typically performed rapidly at this temperature. The flow of the acid solution through the column may range from approximately 0.1 total volume (BV) / hour to approximately 1000 BV / h. The pressure may range from atmospheric pressure to approximately 200 psig.

[0053] After the acid solution has passed through the nanocomposite to recover lithium, washing with water may be required to remove excess acid from the surface of the nanocomposite in order to prepare the column for another cycle of stripping lithium from the liquid resource. In some embodiments, several fixed-bed ion exchange columns may be operated in parallel to make the process more efficient. For example, one column may selectively recover lithium from the liquid resource while another column recovers lithium from the nanocomposite in contact with the acid solution, while yet another column is washed with water to prepare the column for the next cycle.

[0054] The nanocomposite materials of this disclosure, methods for preparing them, and their use for extracting and recovering lithium from brine will be better understood by referring to the non-examples below. [Examples]

[0055] The raw materials used in the preparation of the nanocomposite materials according to this disclosure and referenced in the following examples are purchased from Sigma Aldrich and include: commercial (or commercially available) lithium hydroxide (LiOH, ≥98%, MW23.95), titanium dioxide (TiO2, nanopowder, primary particle size of 21 nm, ≥99.5%), zirconium oxide (ZrO2, nanopowder, particle size of <100 nm, MW123.22), and Ludox. AS40 (SiO2, MW60.08, 40 wt% suspension in H2O), lithium chloride (LiCl, ≥99%, MW42.39), potassium chloride (KCl, ≥99%, MW74.55), magnesium chloride (MgCl2·6H2O, MW203.30), aluminum nitrate (Al(NO3)3·9H2O, MW375.13), sodium silicate solution (Na2O: 10.6%; SiO2: 26.5%), and aluminum hydroxide (Al(OH)3MW78.00).

[0056] Example 1. Preparation of lithium titanate nanocomposite material Figure 2 illustrates a general schematic diagram for the preparation of the nanocomposite lithium titanate (Li2TiO3) using a hot water preparation method in a 300 ml Parr reactor. The reaction conditions were 120°C for 36 hours under stirring at 300 rpm, followed by cooling, and then filtration of the resulting product without washing. The reaction for producing the nanocomposite is as follows: 2LiOH + TiO2 → Li2TiO3 + H2O

[0057] The following reaction mixture was prepared using a lithium-to-titanium molar ratio of 2.2: Lithium hydroxide 6.48g Nano titanium dioxide 9.9g Deionized water 180g

[0058] The crystallinity of the obtained nanocomposite material was confirmed using X-ray diffraction (XRD) and found to be cubic Li2TiO3, as shown in Figure 3. The average crystalline domain size (or crystalline region size, crystalline domain size, crystallized region size, or crystalline domain size) was estimated using Scherrer's equation executed in the PDXL program, showing an average value of approximately 39 nm ± 4 nm. The microstructure properties of the nanomaterial were analyzed by Brunauer-Emmett-Teller (BET), and the results are shown in Table 2. Figure 4 illustrates a scanning electron microscope (SEM) image of this synthesized nanocomposite material. The average nanoparticle size was estimated using different characterization techniques and is compared in Table 1 below. There is no variability in the particle size between the two estimates obtained by XRD and SEM, both in the nanoscale range.

[0059] [Table 1]

[0060] [Table 2]

[0061] Example 2. Preparation of another phase of the lithium titanate nanocomposite material by calcination of the lithium titanate nanomaterial of Example 1 at 450°C. Nanomaterials were prepared in a manner similar to that shown in Example 1, and the resulting dried solids were calcined in a furnace at 450°C for 6 hours. Figure 5 shows the XRD pattern of the calcined Li2TiO3, which is different from that of the product obtained in Example 1. As shown in Figure 5, the pattern of the product in Example 2 is different from that of the product in Example 1. Figure 6 shows an SEM image of the calcined Li2TiO3 from Example 2. The BET measurements are shown in Table 3 below. Although the crystal structure of the product in Example 2 changed, the average crystal domain size and morphology did not change compared to that of Example 1.

[0062] [Table 3]

[0063] Example 3. Preparation of another phase of lithium titanate nanomaterial by calcination of lithium titanate from Example 1 at 650°C. The preparation of this nanocomposite material was similar to that described in Example 1, except that the product was calcined in a furnace at 650°C for 6 hours instead of 450°C as in Example 2. Figure 7 shows the XRD pattern. Figure 8 shows the SEM image of the calcined Li2TiO3. The BET measurements are shown in Table 4 below. The crystalline morphology of this product was found to have changed slightly.

[0064] [Table 4]

[0065] Example 4. Preparation of lithium silicate nanocomposite material The preparation procedure for the nanocomposite lithium silicate (Li2SiO3) was carried out in the same manner as the hot water preparation method used in Example 1. The reaction conditions were 80°C for 72 hours under stirring at 300 rpm, and the resulting product was not washed. The reaction for producing this nanocomposite material is as follows: 2LiOH + SiO2 → Li2SiO3 + H2O

[0066] The following reaction mixture was prepared using a lithium-to-silicon molar ratio of 2.2: Lithium hydroxide 7.8g Ludox AS40 22.5g Deionized water 180g

[0067] The obtained crystalline material was analyzed using X-ray diffraction (XRD). The pattern shown in Figure 9 indicates the formation of Li2SiO3. The obtained crystalline material was analyzed using the Brunauer-Emmett-Teller (BET) method, and the measured values ​​of Li2SiO3 are shown in Table 5 below. Figure 10 shows a scanning electron microscope (SEM) image of the crystalline material.

[0068] [Table 5]

[0069] Example 5. Preparation of another phase of lithium titanate nanocomposite material by calcination of lithium silicate nanomaterial from Example 4 at 750°C. The preparation of this nanomaterial was similar to that described in Example 4, except that after hydrothermal crystallization, the dried solid was calcined in a furnace at 750°C for 6 hours. Figure 11 shows the XRD spectrum of calcined Li2SiO3 having the same crystal structure but different crystalline domains (the signal is not as broad as that found for Example 4). The BET measurements are shown in Table 6 below. Figure 12 illustrates the SEM image of calcined Li2SiO3.

[0070] [Table 6]

[0071] Example 6. Preparation of lithium zirconate nanocomposite material The nanocomposite material, lithium zirconate (Li2ZrO3), was prepared using a solid-phase reaction in a furnace. The reaction conditions were 650°C for 6 hours, and no washing was performed. The reaction of this nanocomposite material was as follows: 2LiOH + ZrO2 → Li2ZrO3 + H2O

[0072] To produce the paste, the following reaction mixture was prepared using a lithium-to-zirconium molar ratio of 2.0 and sufficient water: Lithium hydroxide 2.31g Zirconium oxide 6g Deionized water 10g

[0073] The obtained nanomaterials were analyzed using X-ray diffraction (XRD), and the resulting patterns are shown in Figure 13.

[0074] Example 7. Preparation of an aluminum-doped lithium silicate nanocomposite material having the lithium silicate structure of Example 4. The procedure for preparing aluminum-doped lithium nanosilicate (Al-doped Li2SiO3) using a hot water preparation method was carried out in 300 ml of Parr. The reaction conditions were 180°C for 60 hours under stirring at 300 rpm. After the reaction was complete and the mixture cooled, the resulting solid was filtered, washed with water, and dried to obtain the Al-doped lithium silicate according to this disclosure.

[0075] The following reaction mixture was prepared using a lithium-to-silicon molar ratio of 4.8 and a silicon-to-aluminum molar ratio of 2.0: Lithium hydroxide 17.244g Ludox AS40 22.5g Aluminum hydroxide 5.842g Deionized water 180g

[0076] The obtained crystalline material was analyzed using X-ray diffraction (XRD), and the pattern is shown in Figure 14, confirming the formation of Al-doped Li2SiO3. The material was analyzed using the Brunauer-Emmett-Teller (BET) method, and the measured values ​​of Al-doped Li2SiO3 are shown in Table 6 below.

[0077] [Table 7]

[0078] Example 8. Preparation of lithium aluminosilicate nanocomposite material This example demonstrates a method for preparing lithium aluminosilicate having a β-spodumene (β-LiAlSi2O6) structure. The preparation involved a combination of precipitation and heat treatment. The following reactants were used for precipitation: Sodium silicate solution 34.523g Aluminum nitrate 28.914g Sodium hydroxide 15.062g Deionized water (1) 100g Concentrated sulfuric acid 12.541g Lithium hydroxide 1.803g Deionized water (2) 15g

[0079] An acidic solution of sulfuric acid was prepared from deionized water (1) and concentrated sulfuric acid. Next, aluminum nitrate and sodium silicate were dissolved in the acidic solution. Sodium hydroxide was gradually added to induce a precipitate of aluminosilicate until a precipitate gel formed at a pH of approximately 8. The precipitate was filtered and washed with deionized water until sulfates were detected. After the wet cake no longer showed the presence of sulfates, it was placed in a beaker and mixed with a solution of lithium hydroxide dissolved in deionized water (2). After homogenization of this solution, the beaker was placed in an 80°C furnace until the mixture was completely dry. The amorphous material was placed in a crucible and then in the furnace and calcined at 850°C for 2 hours. After cooling, the obtained crystalline material was analyzed using X-ray diffraction (XRD). The pattern shown in Figure 15 indicates the formation of β-LiAlSi2O6. Furthermore, the material was analyzed using the Brunauer-Emmett-Teller (BET) method, and the measured values ​​for β-LiAlSi2O6 are shown in Table 7.

[0080] [Table 8]

[0081] Example 9. Activation and Recovery In this example, the solids produced in Examples 1 and 2 were activated using a 1.2 M nitric acid solution. For each test, approximately 1 gram of the solid from Example 1 or 2 (containing approximately 126.5 mg of Li per gram of Li2TiO3) was exposed to 15 mL of the acid solution at room temperature for a predetermined time (1 minute to 1440 minutes). The mixture was filtered, and the recovered solution was tested to determine the amount of lithium extracted from the activated solid by ICP. Ion exchange of lithium ions by proton ions was confirmed by ICP, and the results are shown in Table 8. It can be seen that a very short time is required to recover up to 95% of the expected lithium from the nanocomposite materials of this disclosure tested. Therefore, their activation was carried out in this manner.

[0082] [Table 9]

[0083] Example 10 Activation and Recovery In this example, 0.5 grams each of the nanocomposite materials from Example 3 and Example 8 were mixed with 0.456 g and 0.134 g of 98% concentrated sulfuric acid, respectively. The mixtures were placed in a furnace for heat treatment at 250°C for 30 minutes. After cooling, the solids were dispersed in deionized water to recover lithium as a solution of lithium sulfate. The solids were then filtered, dried, and thus activated. The solution was recovered by filtration at known concentrations of lithium sulfate to be tested by ICP. Ion exchange of lithium ions by proton ions was confirmed by ICP, and the results are shown in Table 9. Depending on the material used, it can be seen that up to 90% of the expected lithium can be recovered from the nanocomposite materials of this disclosure tested.

[0084] [Table 10]

[0085] Example 11. Preparation of a larger batch of lithium titanate nanocomposite material This example demonstrates the preparation of a nanomaterial composite lithium titanate (Li2TiO3) similar to that in Example 1, but in this case, a 1-gallon Parr reactor is used to produce enough material to test the extraction of lithium from a liquid resource. The reaction conditions were 120°C for 36 hours with stirring at 150 rpm, followed by cooling, and then filtering the resulting product without washing.

[0086] The following reaction mixture was prepared using a lithium-to-titanium molar ratio of 2.2: Lithium hydroxide 81.65g Nano titanium dioxide 124.74g Deionized water 2,268g

[0087] The crystallinity of the obtained nanocomposite material was confirmed by X-ray diffraction (XRD) and found to be cubic Li2TiO3, as shown in Figure 16. The average crystal domain size was estimated using Scherrer's equation performed in the PDXL program and showed an average value of approximately 37 nm ± 5 nm. A portion of the material was calcined at 550°C for 6 hours, and the XRD data shown in Figure 17 confirmed the change in the original structure. The microstructure properties of the nanomaterial were analyzed by Brunauer-Emmett-Teller (BET), and the results are shown in Table 10, compared with the uncalcined nanomaterial. A small amount of the calcined material was taken and activated in the same manner as described in Example 9, and infrared spectra of the calcined sample before and after activation were obtained, as shown in Figure 18, with approximately 3200 cm⁻¹ after the activation process. -1 and 885cm -1 The appearance of two strong signals (or signals) clearly indicates a favorable improvement in the internal structure of the nanomaterial by substituting lithium ions with proton ions, making the nanomaterial usable for lithium capture from liquid resources.

[0088] [Table 11]

[0089] Example 12. Preparation of extruded composite materials of lithium titanate nanomaterial (nonmaterial) for application as a lithium removal sorbent from liquid resources. This example demonstrates the preparation of a lithium titanate (Li2TiO3) nanocomposite material containing silica for the production of a solid for lithium extraction from liquid resources and its use in a column bed. 166.6 grams of the uncalcined material from Example 11 was mixed with a solution prepared by diluting 61.2 grams of sodium silicate with 46.7 mL of deionized water. The formed paste was extruded into a spaghetti-like shape using a proprietary stainless steel extruder. The extruded material was dried overnight at room temperature. The extruded material was cut into pieces approximately 1 cm in length (or less), then placed in a stainless steel tray and dried at 100°C for 6 hours, and then calcined at 550°C for 6 hours with a heating gradient of 5°C / min. 162.1 g of silica nanocomposite material adsorbent was recovered and placed in a sealed plastic container for further use.

[0090] Example 13. Use of silica nanocomposite extruded material for lithium removal from liquid resources This example demonstrates the use of a lithium titanate (Li2TiO3) nanocomposite material with silica in a column bed for lithium extraction from a liquid resource. 150 grams of the extruded composite material from Example 12 was packed into a column having a diameter of 1.25 inches and a height of 13 inches. The nanomaterial in the column was activated with a 1 M nitric acid solution, for example, as shown in Figure 1, using a recirculation method at a flow rate of 2.3 L / min at room temperature for 2 hours. After activation, the liquid was removed and the column was washed with deionized water. Next, a brine with a composition of 1200 ppm Li, 1000 ppm Ca, 1000 ppm K, and 1000 ppm Mg was flowed through the column at a flow rate of 2.3 L / min at room temperature for 6 hours using a recirculation method. After this, the brine was removed from the system and the column was cleaned with deionized water. After purifying with water, lithium was recovered from the sorbent using a 0.36 M nitric acid solution at a flow rate of 2.3 L / min over 2 hours at room temperature using a recirculation method. The recovered lithium-rich solution was placed in a rotary evaporator where water was removed and the salt crystallized. The recovered solid was further dried overnight in a furnace at 120°C to recover 23 grams of lithium nitrate salt. Figures 19 and 20 show the XRD pattern and DSC-TGA of the recovered LiNO3 salt (which has a melting point of approximately 254.3°C and a decomposition temperature above 600°C), respectively.

[0091] While the foregoing is intended for various embodiments of the present disclosure, other and further embodiments of the present disclosure may be conceived without departing from its basic scope, the scope of which is determined by the following claims. Furthermore, the disclosure of the present invention may include the following embodiments. (Aspect 1) It is a nanocomposite material, A nanocomposite material having a domain size of less than 100 nm, obtained by mixing at least one lithium source and at least one other source selected from a silicon source, an aluminum source, a titanium source, a zirconium source, a metal phosphate source, and a mixture thereof in an aqueous medium to form a suspension with an atomic molar ratio of at least 2.0:1 of lithium to the other source; subjecting the suspension to a hot water treatment to form a nanocomposite material; and optionally subjecting the nanocomposite material to a heat treatment. (Aspect 2) The nanocomposite material according to embodiment 1, wherein the hot water treatment includes subjecting the suspension to a temperature of approximately 60°C to approximately 250°C for a period of time of approximately 1 hour to approximately 84 hours. (Aspect 3) The nanocomposite material according to embodiment 1, wherein the lithium source is lithium chloride, lithium hydroxide, lithium nitrate, lithium sulfate, lithium carbonate, or a mixture thereof. (Aspect 4) The nanocomposite material according to embodiment 1, wherein the other source is titanium dioxide, zirconium oxide, silicon dioxide, aluminum nitrate, sodium silicate, aluminum hydroxide, sodium silicate, iron phosphate, zinc phosphate, zinc phosphate, manganese phosphate, or magnesium phosphate. (Appendix 5) The nanocomposite material according to embodiment 4, wherein the other source is first treated with an acid or base for the formation of a homogeneous precipitate or smooth gel that can be washed and dried. (Aspect 6) The nanocomposite material according to embodiment 5, wherein the acid is selected from nitric acid, hydrochloric acid, sulfuric acid, and carboxylic acid. (Aspect 7) The nanocomposite material according to embodiment 5, wherein the base is selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, and ammonia. (Pattern 8) The nanocomposite material according to embodiment 1, wherein the nanocomposite material has domain sizes between approximately 10 nm and approximately 90 nm. (Aspect 9) The nanocomposite material according to embodiment 1, wherein the nanocomposite material is subjected to heat treatment at a temperature of approximately 100°C to approximately 1050°C for a period of time of approximately 1 hour to approximately 84 hours. (Aspect 10) The nanocomposite material according to embodiment 1, wherein the nanocomposite material is composited with an inorganic or organic binder or aggregate. (Aspect 11) A method for producing a lithium salt from a liquid resource, comprising: (i) placing a nanocomposite material according to embodiment 1 in a column; then contacting the nanocomposite material with a first acid solution to exchange lithium ions in the nanocomposite material with hydrogen ions and activate the nanocomposite material; (ii) passing the liquid resource through the column to selectively extract lithium from the liquid resource to form a lithium-rich nanocomposite material; and (iii) contacting the lithium-rich nanocomposite material with a second acid solution to produce a lithium salt. (Aspect 12) The method according to embodiment 11, further comprising recovering the lithium salt. (Aspect 13) A lithium salt recovered according to the method described in Embodiment 12. (Aspect 14) A method for producing a lithium salt from a liquid resource, comprising: (i) providing a fixed-bed ion exchange column containing a nanocomposite material according to Embodiment 1; (ii) contacting the nanocomposite material with an acid to replace lithium ions with hydrogen ions; (iii) contacting the nanocomposite material in the fixed-bed ion exchange column with a liquid resource to selectively extract lithium from the liquid resource, thereby exchanging hydrogen ions from the nanocomposite material only for lithium ions from the liquid resource to produce a lithium-rich nanocomposite material; and (iii) contacting the lithium-rich nanocomposite material with an acid solution to exchange lithium ions from the lithium-rich nanocomposite material for hydrogen ions from the acid solution to produce a lithium salt. (Aspect 15) A nanocomposite material obtained by mixing at least one lithium source and a colloidal silica solution in an aqueous medium to form a suspension having an atomic molar ratio of lithium to silica of at least 2.0:1, and subjecting the suspension to a hot water treatment to form a nanocomposite material. (Aspect 16) The nanocomposite material according to embodiment 15, wherein the hot water treatment includes subjecting the suspension to a temperature of approximately 60°C to approximately 250°C for a period of time of approximately 1 hour to approximately 84 hours. (Aspect 17) The nanocomposite material according to embodiment 16, wherein the nanocomposite material is further subjected to heat treatment at a temperature of approximately 100°C to approximately 1050°C for a period of time of approximately 1 hour to approximately 84 hours. (Aspect 18) The nanocomposite material according to embodiment 15, wherein an aluminum salt is mixed with the lithium source and the colloidal silica solution to form the suspension. (Aspect 19) The aforementioned aluminum salt is Al(NO 3 ) 3 or Al(OH) 3 A nanocomposite material according to embodiment 18, including the above. (Aspect 20) The nanocomposite material according to embodiment 19, wherein the lithium supply source contains lithium hydroxide. (Aspect 21) The nanocomposite material according to embodiment 20, wherein the nanocomposite material includes an Al-doped lithium silicate nanocomposite material. (Aspect 22) It is a nanocomposite material, The material is obtained by mixing at least one lithium source and a metal phosphate source in an aqueous medium to form a suspension having an atomic molar ratio of at least 2.0:1 of lithium to the metal of the metal phosphate source, and by subjecting the suspension to a hot water treatment to form a nanocomposite material, wherein the metal of the metal phosphate source is Fe 2+ Zn 2+ Co 2+ Cu 2+ Mn 2+ Ni 2+ , and nanocomposite materials selected from mixtures thereof. (Aspect 23) The nanocomposite material according to embodiment 22, wherein the suspension is placed in a reactor and subjected to hot water treatment at a temperature of approximately 65°C to approximately 200°C for a period of approximately 1 hour to approximately 84 hours to produce a lithium metal phosphate nanocomposite material, and further subjected to heat treatment of the lithium metal phosphate nanocomposite material at a temperature of approximately 100°C to approximately 1050°C for a period of approximately 1 hour to approximately 84 hours.

Claims

1. A method for producing a nanocomposite material for lithium extraction, wherein the method is: Mixing at least one lithium source with at least one other source selected from a silicon source, an aluminum source, a titanium source, a zirconium source, a metal phosphate source, and mixtures thereof in an aqueous medium to form a suspension with an atomic molar ratio of at least 2.2:1 of lithium to the other source. The suspension is subjected to hot water treatment at a temperature of 60°C to 250°C for a period of 1 to 84 hours to form a nanocomposite material, and The process includes subjecting the nanocomposite material to heat treatment at a temperature of 100°C to 1050°C for a period of time from 1 hour to 84 hours. The nanocomposite material has domain sizes ranging from 10 nm to 90 nm.

2. The lithium source is lithium chloride, lithium hydroxide, lithium nitrate, lithium sulfate, lithium carbonate, or a mixture thereof, and The method according to claim 1, wherein the other source is titanium dioxide, zirconium oxide, silicon dioxide, aluminum nitrate, sodium silicate, aluminum hydroxide, iron phosphate, zinc phosphate, manganese phosphate, or magnesium phosphate.

3. For the formation of a precipitate or gel that can be washed and dried, the other source is first treated with an acid or base, The acid is selected from nitric acid, hydrochloric acid, sulfuric acid, and carboxylic acid. The method according to claim 2, wherein the base is selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, and ammonia.

4. The method according to claim 1, wherein the nanocomposite material further comprises a doping element selected from Al, Ti, Zr, Si, Fe, Mn, Zn, Co, Cu, P, or a mixture thereof, and has a domain size between 20 nm and 60 nm.

5. The method according to claim 1, wherein the nanocomposite material is compounded with an inorganic or organic binder or aggregate.

6. A method for producing lithium salts from liquid resources, (i) Mixing at least one lithium source with at least one other source selected from a silicon source, an aluminum source, a titanium source, a zirconium source, a metal phosphate source, and mixtures thereof in an aqueous medium to form a suspension having an atomic molar ratio of at least 2.2:1 of lithium to the other source; (ii) Forming a nanocomposite material by subjecting the suspension to hot water treatment at a temperature of 60°C to 250°C for a period of 1 to 84 hours; (iii) The nanocomposite material is subjected to heat treatment at a temperature of 100°C to 1050°C for a period of time of 1 hour to 84 hours, wherein the nanocomposite material has domain sizes of 10 nm to 90 nm; (iv) Placing the nanocomposite material in a column, and then contacting the nanocomposite material with an acid solution to exchange lithium ions in the nanocomposite material for hydrogen ions and activate the nanocomposite material; (v) Passing the liquid resource through the column to selectively extract lithium from the liquid resource and form a lithium-rich nanocomposite material; (vi) bringing the lithium-rich nanocomposite material into contact with an acid solution to produce a lithium salt; and (vii) A method comprising recovering the lithium salt.

7. The method according to claim 6, The column is a fixed-bed ion exchange column. A method comprising the exchange of hydrogen ions from the nanocomposite material for lithium ions from the liquid resource to produce the lithium-rich nanocomposite material.

8. The method according to claim 1, wherein the nanocomposite material is obtained by mixing at least one lithium source and a colloidal silica solution in an aqueous medium to form the suspension having an atomic molar ratio of lithium to silica of at least 2.2:1, and subjecting the suspension to a hot water treatment to form the nanocomposite material.

9. The method according to claim 8, wherein the aluminum salt is mixed with the lithium source and the colloidal silica solution to form the suspension.

10. The aforementioned aluminum salt is Al(NO) ３ ) ３ or Al(OH) ３ Includes, The lithium supply source includes lithium hydroxide, The method according to claim 9, wherein the nanocomposite material includes an Al-doped lithium silicate nanocomposite material.

11. The method according to claim 1, The nanocomposite material is formed by mixing at least one lithium source and a metal phosphate source in an aqueous medium to form a suspension with an atomic molar ratio of at least 2.2:1 of lithium to the metal of the metal phosphate source, The above suspension is subjected to hot water treatment to form a nanocomposite material, The metal of the metal phosphate source is Fe ２＋ , Zn ２＋ , Co ２＋ , Cu ２＋ , Mn ２＋ , Ni ２＋ , and a method selected from mixtures thereof.

12. The method according to claim 11, wherein the suspension is placed in a reactor and subjected to hot water treatment at a temperature of 65°C to 200°C for a period of 1 to 84 hours to produce a lithium metal phosphate nanocomposite material, and further subjected to heat treatment of the lithium metal phosphate nanocomposite material at a temperature of 100°C to 1050°C for a period of 1 to 84 hours.

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