Systems and methods for producing metals from brine solutions

Abstract

Methods and systems for the direct production of lithium and other metals at room temperature from saline solutions containing various metal cation salts by combining adsorbent extraction and electrochemical extraction / electroplating processes. The skeleton structure material used in the process can reversibly insert / extract the required metal cations so as to absorb the required metal ions from the saline solution. The metal-impregnated skeletal structure material is then transferred into an electrochemical cell, metal ions are extracted from the structure and plated onto an electronically conductive substrate in the form of a metal. The process is a combination of a plurality of methods for directly extracting metal ions from an aqueous brine solution to produce a metal end product, significantly improved compared to current processes, and capable of reducing the energy required for metal production.

Description

[0001] This application claims priority to U.S. Provisional Application No. 63 / 327,231, filed on April 4, 2022, the entire contents of which are hereby incorporated by reference. Technical Field

[0002] The present disclosure generally relates to methods for producing metals at or near room temperature. More specifically, the present disclosure relates to methods for producing metals from brine solutions at or near room temperature. Background Art

[0003] In the case of lithium, the typical commodities are lithium hydroxide monohydrate (also loosely referred to as lithium hydroxide or LiOH) and lithium carbonate (Li2CO3). Both of these chemicals are very important industrially as precursor chemicals for lithium-ion battery cathode materials. With the growing demand and production of electric vehicles, not only is the demand for these commodities growing, but a market for lithium in metallic form has also emerged. This sudden demand stems from the emergence of a new generation of battery chemistries that can use metallic lithium as anodes in secondary lithium batteries with higher energy and power densities than current lithium-ion technologies. However, current lithium metal production methods must be improved to meet the upcoming lithium metal demand and to achieve production targets when these battery chemistries are commercialized.

[0004] Currently, the molten salt electrolysis process is used to produce lithium metal and its various alloys. The electrolytic cell of this process consists of a stainless steel cathode, a graphite anode and a eutectic KCl-LiCl electrolyte. The process is carried out at a temperature of about 400-500°C, and metallic lithium with a purity of more than 97% can be obtained. The high temperatures required to carry out the electrolysis process are energy-intensive, and the side reaction of forming metallic lithium at the cathode is the production of an undesirable and highly toxic chlorine gas (Cl2) as a by-product. Other alkali metals or alkaline earth metals require high temperature treatment, such as molten salt electrolysis for potassium, carbothermal reduction for sodium, or silicon thermal process for magnesium. Other alkali metals or alkaline earth metals require high temperature treatment, such as molten salt electrolysis for potassium, carbothermal reduction for sodium, or silicon thermal process for magnesium. Summary of the invention

[0005] The present disclosure provides methods and systems for producing metals directly from brine solutions composed of solvated salts containing various cations and anions. A skeleton or framework material is placed in a brine solution to allow it to accept metal ions, such as lithium ions, and then placed in a compatible electrolyte solution, in which the metal ions can be removed and plated onto a substrate as a metal, such as lithium metal on copper. The method can use any skeleton or framework structure that can reversibly embed / de-embed the relevant metal ions and is stable in a brine solution and a suitable electrolyte solution. In addition, the present invention also includes a device for this process that can selectively extract metal ions from a brine solution containing a single or multiple different cation salts and plate them into the desired metal, so that the only input of the device is a brine solution containing metal ions with any type of counter anion, and the product output of the device is a metal. The method and the device for performing the method can work in a batch or continuous process.

[0006] As far as lithium metal is concerned, further improvements to the system could produce battery-grade lithium metal - perhaps in a roll-to-roll manner, and possibly in an acceptable form for use as lithium battery anodes. Currently, the initial idea is to produce crude lithium metal (purity greater than 90%) from aqueous lithium brine solutions. These further improvements in producing battery-grade lithium metal could also be applied to the production of high-purity metals required for other secondary battery applications, such as sodium, potassium or magnesium.

[0007] Other objects, features and advantages of the present disclosure will be apparent from the following detailed description. However, it should be understood that the detailed description and specific examples, while indicating specific embodiments of the present disclosure, are given by way of illustration only, as various changes and modifications within the spirit and scope of the present disclosure will become apparent to those skilled in the art from the detailed description. Note that simply because a particular compound is attributed to one particular general formula does not mean that it cannot also belong to another general formula. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] In order to understand in more detail the features, advantages and purposes of the present invention and how other features, advantages and purposes that may be apparent are achieved, the present invention briefly summarized above may be described in more detail with reference to the embodiments in the accompanying drawings, which form a part of this specification. It should be noted, however, that the drawings illustrate only exemplary embodiments of the present invention and are therefore not to be considered as limiting the scope of the present invention, as the present invention may accommodate other equally effective embodiments.

[0009] Figure 1 Schematic diagram of the overall disclosed method of going from brine to lithium metal using a reusable sorbent framework material.

[0010] Figure 2Schematic diagram of one embodiment of the disclosed method for converting brine to lithium metal using a reusable sorbent framework material.

[0011] Figure 3 Schematic diagram of one embodiment of the disclosed method for converting brine to lithium metal using a reusable sorbent framework material.

[0012] Figure 4 A detailed schematic diagram of the overall process of extracting lithium ions from a brine solution into a lithium metal final product.

[0013] Figure 5 Schematic diagram of the equipment for continuous direct production of lithium metal from brine solution.

[0014] Figure 6 Schematic diagram of a device for mass production of metallic lithium directly from brine solution - if many cells are connected in series, the device can be set up as a continuous production process.

[0015] Figure 7 Schematic diagram of the composite electrode matrix used to embed the adsorbent material and transfer between the stages of the extraction and metal plating processes.

[0016] Figure 8 Isometric view of the test cell setup for the proof-of-concept experiments performed in Example 2.

[0017] Fig. 9 Top view of the test cell setup for the proof-of-concept experiments performed in Example 2.

[0018] Fig.10 Front view of the test cell setup for the proof-of-concept experiments performed in Example 2.

[0019] Fig.11 Complete experimental setup for the proof-of-concept run in Example 2.

[0020] Fig.12 is the starting electronically conductive substrate - in this case copper foil - prior to the lithium metal plating step.

[0021] Fig.13 It is a plated metal on an electronically conductive substrate - in this case lithium metal on copper foil.

[0022] Fig.14 A scanning electron microscope image of purchased lithium metal produced by traditional manufacturing methods and rolled into full metal foil.

[0023] Fig.15 is a scanning electron microscope image of a lithium metal anode plated on copper produced by the method disclosed herein.

[0024] Fig.16 X-ray photoelectron spectra of purchased lithium metal produced by conventional manufacturing methods and rolled into full metal foil (T sample) and lithium metal anode deposited on copper produced by the method disclosed herein.

[0025] Fig.17 Graph showing the relationship between cycle number and specific capacity for a battery consisting of a LiFePO4-based cathode and a lithium metal anode produced by the method disclosed herein. DETAILED DESCRIPTION

[0026] The present disclosure provides a method for producing metals directly from a brine solution, wherein the brine solution is an aqueous solution composed of salts of a plurality of different cations. Figure 1-3 The entire process and variations of different embodiments of the disclosed method are shown in FIG. 1 . In the case of lithium, in contrast to current industrial methods of lithium metal production (which must be carried out at temperatures ranging from 400° C. to 500° C. and produce toxic chlorine gas (Cl 2(g) ) as a byproduct), the disclosed method can be carried out entirely at room temperature and does not produce any toxic byproducts. In addition, the disclosed method requires an apparatus to carry out the adsorbent extraction and metal electrodeposition processes in series in a continuous manner. If the starting brine solution contains metal cations of a specific metal, any related metal can be obtained by this process. The metals to which this process can be applied include, but are not limited to, sodium, potassium or magnesium.

[0027] Combining adsorbent extraction with electrodeposition of metals in non-aqueous media requires a framework material that is capable of reversibly inserting / extracting the final desired metal ions. In order to produce metals from brine solutions, the adsorbent framework material must be capable of reversibly inserting / extracting metal ions. The adsorbent framework material must be stable in brine solutions and capable of inserting metal ions into brine solutions. In addition, due to the reactivity of certain potential final metal products (such as lithium metal), the metal-impregnated adsorbent framework material must be stable in non-aqueous electrolyte media and have the ability to electrochemically extract metal ions therefrom. For ease of illustration, the case of lithium metal production will be discussed in the remainder of this disclosure, with the understanding that it can replace any relevant metal with cations present in the starting brine solution.

[0028] The adsorbent extraction mechanism of the framework material for the intercalation of lithium ions into the brine solution may include, but is not limited to, concentration-driven intercalation, chemical reduction / oxidation reactions, electrochemical reduction / oxidation reactions, or a combination thereof. The adsorbent framework structure refers to a crystalline material having the ability to selectively insert / extract lithium ions relative to other ions present in the brine solution (e.g., sodium, potassium, magnesium, and calcium). These materials may also include transition metal complexes that form a framework using coordination complexes that allow selective binding of lithium ions. In some embodiments, these complexes may preferentially bind lithium ions rather than other ions, such as calcium ions, magnesium ions, potassium ions, or sodium ions. In other embodiments, these adsorbent framework structures may be first complexed to the adsorbent framework structure, and then the lithium is removed by a delithiation process, so that the resulting adsorbent structure can easily absorb new lithium ions from the brine solution. Organic or inorganic materials that can be used for this purpose include, but are not limited to, organosulfur compounds, carbonyl compounds, imine compounds, anatase TiO2, rutile TiO2, Li4Ti5O 12 , LiFePO4 and TiNb2O7. In addition, the adsorption framework material can also be composed of a material that already contains lithium during synthesis and whose crystal structure has reached the maximum capacity, but in this case, a delithiation step is required before the material is used as an adsorbent framework material. The adsorbent framework material is used in the adsorbent extraction step and then washed and dried to prevent contamination of the non-aqueous electrolyte medium, which is required for the last step of the method. After washing and drying, the lithiated framework material is placed in a non-aqueous electrolyte solution, lithium ions are extracted from the framework adsorbent material, and then plated onto an electronically conductive substrate. The method of extracting lithium in the non-aqueous electrolyte medium may include but is not limited to concentration-driven reactions, pressure-driven reactions, chemical reduction / oxidation reactions, electrochemical reduction / oxidation reactions, or a combination thereof.

[0029] The final lithium metal product of the disclosed method can be further processed to produce battery-grade lithium metal. This battery-grade lithium metal can also be further processed into a lithium metal anode for a primary or secondary lithium battery. The disclosed method can also be customized to directly produce battery-grade lithium metal and / or lithium metal anodes that can be directly used in primary or secondary lithium batteries. Such primary or secondary lithium battery chemistries that can use lithium metal anodes directly prepared by the disclosed method include, but are not limited to: Li-MnO2 batteries, Li-O2 batteries, Li-S batteries, batteries with Li[Ni x Mn y Co z ]O2(x+y+z=1), Li[Ni x Co y Al z ]O2(x+y+z=1), Li[Ni x Mn y]O2(x+y=1), Li[Li x Ni y Mn z ]O2(x+y+z=1) or LiFePO4 cathode. The method can be tailored to produce advanced lithium metals or directly produce lithium metal anodes by formulating non-aqueous solvents with solvated lithium conductive salts for extracting lithium ions from the adsorbent framework and plating them onto an electronically conductive substrate.

[0030] Due to the uniqueness of the disclosed combinatorial process, new equipment must be constructed to perform the process from start to finish in either a continuous or batch manner. Figure 5 A schematic diagram of an apparatus that enables a continuous process to produce lithium metal from a brine solution, possibly in a roll-to-roll manner, is shown. In this apparatus, an adsorbent skeleton material is transferred between a brine solution and a non-aqueous solvent having a lithium conductive salt. A washing bath and a drying step are provided between the two main tanks (the brine tank and the non-aqueous solvent tank) to prevent the two systems from contaminating each other. In this design, the brine solution is the only part that must be replenished during use because a lithium source must be continuously provided. However, even the replenishment of the brine can be achieved through a suitable pump system to achieve a continuous process. Figure 6 An apparatus is shown that enables a batch process of the methods described herein. In the apparatus, the adsorbent framework structure remains stationary while the necessary liquids - brine solution, washing solution or non-aqueous solvent containing conductive salts - enter the apparatus depending on the process step being performed. When lithium metal is deposited, the counter electrode is placed in the cell as required. The non-aqueous solvent can be recycled in the apparatus design.

[0031] The mode of transferring or putting the adsorbent skeleton structure into the device depends on the production volume required for the process. In one embodiment of the method and device, the adsorbent skeleton material can be embedded with a conductive additive (such as carbon black, graphene or reduced graphene oxide) and a polymer binder (such as polyvinylidene fluoride (PVDF) or polytetrafluoroethylene (PTFE)). Some non-limiting examples of conductive additives include 0-50wt%. Similarly, non-limiting examples of polymer binders include 0-30wt%. In addition, the composite material can be cast on a substrate. The substrate can be a two-dimensional substrate (such as a metal foil) or a three-dimensional substrate (such as a metal foam). Figure 7 A schematic diagram of one embodiment is shown, in which a composite material of an adsorbent framework material, a conductive additive, and a polymer binder is cast onto a two-dimensional metal foil substrate for Figure 5 and Figure 6 In any of the devices shown in .

[0032] The specification, including the summary of the invention, the accompanying drawings and the detailed description, and the appended claims are directed to specific features (including process or method steps) of the present disclosure. It is understood by those skilled in the art that the present invention includes all possible combinations and uses of the specific features described in the specification. It is understood by those skilled in the art that the present disclosure is not limited to or by the description of the embodiments given in the specification.

[0033] It is also understood by those skilled in the art that the terms used to describe a particular embodiment do not limit the scope or breadth of the present disclosure. In interpreting the specification and the appended claims, all terms should be interpreted in the broadest possible manner consistent with the context of each term. Unless otherwise defined, all technical and scientific terms used in the specification and the appended claims have the same meaning as those commonly understood by those of ordinary skill in the art to which the present invention belongs.

[0034] As used in the specification and the appended claims, the singular forms "one", "a kind of" and "the" include plural references unless the context clearly indicates otherwise. The verb "comprise" and its conjugated forms should be interpreted as referring to an element, component or step in a non-exclusive manner. The quoted element, component or step can exist, use or combine with other elements, components or steps that are not clearly quoted. The verb "operably connectable" and its conjugated forms mean to complete the required engagement of any type, including electricity, machinery or fluid, to form a connection between two or more previously unengaged objects. If the first component is operably connected to the second component, the connection can occur directly or through a common connector. "Optionally" and its various forms mean that the event or situation described subsequently may or may not occur. The description includes instances where an event or situation occurs and instances where the event or situation does not occur.

[0035] Unless specifically stated otherwise, or otherwise understood in the context of use, conditional language such as "can," "may," "might," or "may" is generally intended to convey that some embodiments may include and other embodiments do not include certain features, elements, and / or operations. Thus, such conditional language is generally not intended to imply that one or more embodiments require features, elements, and / or operations in any way, or that one or more embodiments must include logic for determining, with or without user input or prompting, whether such features, elements, and / or operations are included in or will be performed in any particular embodiment.

[0036] Therefore, the systems and methods described herein are well suited to achieve the objects and advantages mentioned, as well as other objects and advantages inherent therein. Although example embodiments of the systems and methods have been given for purposes of disclosure, there are many changes in the details of the processes used to achieve the desired results. These and other similar modifications may be readily appreciated by those skilled in the art, and these and other similar modifications are intended to be included within the spirit of the systems and methods disclosed herein and within the scope of the appended claims.

[0037] Example 1: Olivine FePO4 as an adsorbent framework material for producing lithium metal from brine solutions

[0038] In one embodiment of the present invention, LiFePO4 can be chemically delithiated to form a FePO4 skeleton structure that can be used as a carrier for taking lithium ions from brine solutions and converting them into lithium metal. In order to form the correct crystal structure to reversibly insert / extract lithium ions into it, FePO4 must be synthesized with lithium pre-existing in the LiFePO4. Therefore, for this proof-of-concept experiment, 31.56 g (0.2 mol) of LiFePO4 was mixed with 27.032 g (0.01 mol) of potassium persulfate ((K2S2O8) in water to chemically delithiate the LiFePO4 to FePO4. The solution was mixed for 24 hours to ensure that the structure was completely delithiated. The chemically delithiated FePO4 was allowed to settle to the bottom of the solution for 30 minutes and the powder was collected and tested for lithiation in a real brine solution. The chemically delithiated FePO4 was then placed in a real brine solution and Na2S2O3 was added as a reagent to obtain lithium ions from the brine solution to insert into the FePO4 structure to convert LiFePO4. The proof of lithiation of the FePO4 adsorbent framework material that absorbed lithium from the brine solution was tested using inductively coupled plasma optical emission spectroscopy (ICP-OES) to observe the lithium concentration in the brine solution before and after the FePO4 brine lithiation process.

[0039] Table 1 lists the ICP-OES test results, which provide empirical evidence that chemically delithiated FePO4 can reabsorb lithium ions when placed in a brine solution. After the brine lithiation process, the lithium concentration dropped dramatically, indicating that most of the lithium ions in the brine solution were inserted into the FePO4 framework adsorbent material and converted to LiFePO4. The main problem in extracting lithium from brine solutions is the absorption of magnesium ions. For comparison purposes, Table 1 lists the magnesium content of the brine solution before and after the FePO4 lithiation process. The change in magnesium content in the brine before and after the FePO4 adsorbent extraction was much smaller than the change in lithium content, indicating that the chemically delithiated LiFePO4 adsorbent has an extremely high selectivity for lithium. Other ions of less concern in the brine lithium extraction process are sodium, calcium, and potassium - the concentrations of these ions did not show any significant changes after the brine lithium extraction process. Therefore, the chemically delithiated FePO4 shows an extremely high lithium selectivity in absorbing cations from brine solutions.

[0040] Table 1 Lithium insertion from brine solution into FePO4 chemically delithiated from synthesized LiFePO4

[0041] sample Mg content [ppm] Li content [ppm] <![CDATA[Brine before chemical lithiation of FePO4]]> 1361 862 <![CDATA[Brine after chemical lithiation of FePO4]]> 1220 10

[0042] After the brine lithiation procedure, the chemically delithiated FePO4 (now LiFePO4 after brine lithiation) can be washed and dried to remove any residual salt left over from immersion in the brine solution and transferred to an electrochemical cell to extract lithium ions from the LiFePO4 and plate them as lithium metal onto an electronically conductive substrate. Example 1 is provided to embody Figure 2 The system outlined in .

[0043] Example 2: All-electrochemical method for producing lithium metal from brine solution using compatible adsorbent framework materials

[0044] In one embodiment, if Figure 3 As shown, the presently disclosed method may include an adsorbent extraction and lithium metal deposition process performed electrochemically. Alternatively, if the adsorbent skeleton material is synthesized using a lithium-containing material, the initial delithiation may also be performed electrochemically. For ease of demonstration, this proof-of-concept experiment uses LiFePO4 as the starting material. LiFePO4 is incorporated into an electrode composite material consisting of a conductive additive and a polymer binder material. The composite LiFePO4 electrode is then placed in a Figure 8-10In the electrochemical cell shown, the electrochemical cell contains a non-aqueous solvent with a solvated lithium conductive salt. The LiFePO4 electrode is then electrochemically delithiated to obtain a FePO4 electrode. The FePO4 electrode is then placed in a saline solution and electrochemically lithiated. The re-lithiated LiFePO4 electrode is then placed again in a non-aqueous electrolyte solution to electrochemically extract lithium ions from the LiFePO4 structure and plate them onto a conductive substrate. In practice, for this demonstration, the electrochemical cell is filled with a non-aqueous solvent with a solvated lithium conductive salt for the initial electrochemical delithiation step, filled with saline for the adsorbent framework extraction step, and then the cell is washed with a cleaning solvent so as not to contaminate the cell for the final extraction and electroplating steps performed in a fresh bath of a non-aqueous solvent with a solvated lithium conductive salt. Fig.11 The complete experimental setup for this series of tests is provided. For all electrochemical actuation steps, a power supply was used to provide a constant voltage across the cell. Fig.12 Shown is the starting electronically conductive substrate (copper foil in this case) prior to the lithium metal plating step. Fig.13 2 shows the plated metal on an electronically conductive substrate (lithium metal on copper foil in this case). Table 2 shows the results of the analysis of several cycles performed using the methods and systems described herein. With each cycle of adsorbent extraction and subsequent plating of lithium metal from the lithiated adsorbent material in a separate non-aqueous solvent bath with a lithium conductive salt, the concentration of lithium in the brine decreases. Also provided in Table 2 are the weight and thickness of the plated lithium metal after each cycle, indicating that extremely thin lithium metal can be produced. The thickness and weight of the final metal product produced in each cycle can be further adjusted by the amount of adsorbent framework material used in the production process.

[0045] Table 2 Results of proof-of-concept experiments for producing lithium metal directly from brine solutions using chemically delithiated LiFePO4 (olivine FePO4) frameworks

[0046] cycle Lithium brine (Li) concentration The amount of lithium metal plated per cycle Thickness of lithium metal plated on copper Starting brine 14,135ppm N / A N / A After 1 cycle 13,827ppm 1.48mg 4.51μm After 2 cycles 12,214ppm 1.71mg 5.21μm After 3 cycles 11,338ppm 1.18mg 3.59μm

[0047] Fig.14 The morphology of lithium metal produced by conventional molten salt electrolysis methods that has been rolled into a free-standing foil is shown. Even with extensive processing, the surface is still not completely smooth, and the inhomogeneities provide nucleation sites for dendritic lithium when cycling in a battery. The lithium metal produced by the disclosed method ( Fig.15 ) show extremely large grains, which indicates that dense lithium metal plating is beneficial for use in secondary lithium metal batteries. Fig.16 Further spectroscopic evidence was provided that the metal plated was indeed metallic lithium and not another metal of similar optical qualities. Fig.16 Shows Fig.14X-ray photoelectron spectroscopy (XPS) spectra of a purchased lithium metal sample (sample T) and a lithium metal anode produced by the disclosed method (sample AK) are shown. The similarity of the main peak around about 55 eV proves the presence of metallic lithium in both samples, and the presence of other peaks may be due to surface contamination or replacement lithium products when lithium metal is exposed to various conditions. Since XPS is a surface-sensitive technique that can detect the binding state of chemical species within the first 5-10 nanometers of the sample, these additional peaks are very common.

[0048] To demonstrate the feasibility of the lithium metal anode product produced by the disclosed method, a button cell was prepared using the lithium metal and a commercially available LiFePO4 composite cathode. The cycle of the button cell was Fig.17 As shown in the figure, the battery was started at a low current rate of C / 20 and then iteratively reached a terminal rate of C / 3 for a long time. During the constant current cycling experiment, the battery showed stable cycling and high coulombic efficiency. Therefore, it is shown that the lithium metal anode product produced by the current method can be used as a viable anode in secondary lithium batteries. If it is optimized, the performance indicators of secondary lithium metal batteries can be improved to that expected for batteries using lithium metal anodes instead of traditional graphite anodes.

Claims

1. A method for preparing high-purity metal, comprising: (A) exposing the brine solution to an adsorbent material that absorbs metal ions to form a metal-impregnated adsorbent material; as well as (B) exposing the metal-impregnated adsorbent material to an electric current to obtain a high purity metal and a metal-depleted adsorbent material.

2. The method of claim 1, wherein the metal-impregnated adsorbent material is prepared using a chemical electrochemical process.

3. The method of claim 1, wherein the metal-impregnated adsorbent material is prepared using a concentration-driven process.

4. The method of claim 1, wherein the metal-impregnated adsorbent material is prepared using a pressure-driven process.

5. The method of any one of claims 1-4, wherein the brine solution contains at least 0.3 ppm lithium.

6. The method of claim 5, wherein the brine solution contains one or more impurity metal salts, wherein the impurity metal salts are different from the metal ion.

7. The method of claim 6, wherein the brine solution contains an impurity metal salt selected from lithium salts, calcium salts, magnesium salts, sodium salts, potassium salts, cesium salts, boron salts, barium salts, strontium salts, or combinations thereof.

8. The method according to any one of claims 1 to 7, wherein the adsorbent material is a solid material.

9. The method of claim 8, wherein the adsorbent material is a solid organic material.

10. The method of claim 8, wherein the adsorbent material is a solid inorganic material.

11. The method of any one of claims 1-10, wherein the adsorbent material is a lithium intercalation material.

12. The method of claim 11, wherein the lithium intercalation material is iron phosphate.

13. The method of claim 12, wherein the lithium intercalation material is olivine-structured FePO4.

14. The method according to any one of claims 1 to 13, wherein the adsorbent material is in a solid phase.

15. The method of claim 14, wherein the adsorbent material has a preference for lithium ions relative to other metal ions of at least 10:

1.

16. The method of claim 15, wherein the adsorbent material has a preference of at least 100:

1.

17. The method of any one of claims 1-16, wherein the adsorbent material is immobilized to a surface.

18. The method of any one of claims 1-17, wherein the adsorbent material is produced after exposure to a monovalent or divalent metal consuming solution.

19. The method of claim 18, wherein the metal-consuming solution is a metal sulfate.

20. The method of claim 19, wherein the metal sulfate is potassium persulfate.

21. The method of any one of claims 1-20, wherein the adsorbent material is exposed to brine containing an absorption aid.

22. The method of claim 21, wherein the absorption aid is thiosulfate.

23. A method according to claim 21 or claim 22, wherein the absorption aid is sodium thiosulfate.

24. The method of any one of claims 1 to 23, wherein the metal-impregnated adsorbent material is incorporated into a composite material comprising an electrically conductive material.

25. The method of claim 24, wherein the conductive material is 0-50 wt%.

26. The method of any one of claims 1-25, wherein the metal-impregnated adsorbent material is incorporated into a composite material comprising a polymeric binder.

27. The method of claim 26, wherein the polymer binder is 0-30 wt%.

28. The method of any one of claims 1-27, wherein the metal-impregnated adsorbent material is formulated as an electrode.

29. The method of any one of claims 1-28, wherein the metal-impregnated adsorbent material is placed in a solution with a solvent and an electrolyte.

30. The method of claim 29, wherein the solvent is a non-aqueous solvent.

31. A method according to claim 29 or claim 30, wherein the electrolyte is a solvated metal ion conducting salt.

32. The method of any one of claims 1-31, wherein the electric current is passed between the metal-impregnated adsorbent material and a second electrode.

33. The method of claim 32, wherein the second electrode allows for metal deposition.

34. The method of claim 33, wherein the second electrode is capable of electroplating a metal.

35. The method of any one of claims 1 to 34, wherein the method is configured to allow for continuous deposition of metal.

36. The method of any one of claims 1-34, wherein the method is configured to allow the metal to be deposited on a substrate.

37. The method of any one of claims 1-36, wherein the method allows for roll-to-roll deposition.

38. The method of any one of claims 1-37, wherein the method comprises washing the monovalent or divalent metal-depleted adsorbent material with a washing solution to obtain a purified, depleted adsorbent material.

39. The method of claim 38, wherein the washing solution is ethanol or water.

40. The method of any one of claims 1-39, wherein the method further comprises drying the purified, exhausted adsorbent material to obtain a dried purified, exhausted adsorbent material.

41. The method of any one of claims 1-40, wherein the method comprises exposing the delithiated sorbent material to a second brine solution.

42. An apparatus for preparing metal, comprising: (A) adsorbent material; (B) a first chamber, wherein the first chamber comprises one or more sealable openings for introducing a fluid; (C) an electrode for depositing metal; and (D)Power supply.

43. The device of claim 42, wherein the adsorbent material is deposited onto the second electrode.

44. Apparatus according to claim 42 or claim 43, wherein: The sealable opening is configured to fill the first chamber with saline.

45. The device according to any one of claims 42 to 44, wherein The sealable opening is configured to empty the first chamber of saline.

46. ​​The device of any one of claims 42-45, wherein the sealable opening is configured to introduce a non-aqueous solvent.

47. The device of claim 46, wherein the non-aqueous solvent further comprises an electrolyte.

48. The device of any one of claims 42-47, wherein the electrode, the second electrode, and the power source are configured to allow energy to flow from the power source to the electrode and the second electrode.

49. The device of any one of claims 42-48, wherein the device further comprises a second chamber.

50. The apparatus of claim 49, wherein the second electrode is configured to rotate between the chamber and the second chamber.

51. An apparatus according to claim 49 or claim 50, wherein the second electrode is configured to pass a wash solution between the chamber and the second chamber.

52. The device of any one of claims 42-51, wherein the first chamber is configured to introduce a wash solution into the chamber.

53. The device of claim 52, wherein the first chamber is configured to remove the wash solution from the chamber.

54. The apparatus of any one of claims 42-53, wherein the electrodes are configured to allow continuous metal electroplating.

55. The apparatus of any one of claims 42-53, wherein the electrodes are configured to allow metal electroplating in a roll-to-roll process.

56. The device of any one of claims 42-55, wherein the second electrode further comprises an additive to enhance the electronic conductivity of the composite material.

57. The device of any one of claims 42-56, wherein the second electrode further comprises a polymer binder.

58. The device according to any one of claims 42 to 57, wherein the device further comprises an element for drying the adsorbent material.

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