Systems and methods for lithium electrodeposition from brine

Abstract

In some aspects, the present disclosure provides a flexible conductive composite membrane. In some embodiments, the composite membrane comprises a hydrophobic film layer and one or more lithium ion conductive particles. In some embodiments, the one or more lithium ion conducting particles each provide an exposed particle surface on two sides of the hydrophobic film layer. In some embodiments, composite membrane is substantially impermeable to water and is configured to provide a Li+ conductivity of at least about 1.0 × 10-6 S / cm through the composite membrane.

Description

Atty Dkt No.: 65848-720601 SYSTEMS AND METHODS FOR LITHIUM ELECTRODEPOSITION FROM BRINE CROSS-REFERENCE

[0001] This application claims the benefit of U.S. Provisional Application No.63 / 578,935, filed August 25, 2023, and U.S. Provisional Application No.63 / 559,727, filed February 29, 2024, each of which is incorporated herein by reference in its entirety. BACKGROUND

[0002] In the lithium electrodeposition process from a brine solution, water present in the brine poses challenges. It can react with lithium to form lithium hydroxide and hydrogen, which can not only lead to wastage but also create safety concerns. Furthermore, water can interfere with the electrodeposition process by leading to the formation of a solid-electrolyte interphase (SEI) layer on the lithium electrode. Although this layer can shield lithium from direct contact with the electrolyte, preventing potential side reactions, it can degrade over time, reducing the efficiency of the process. To address this, focus has been placed on the dehydration of the brine to achieve water-free lithium deposition, thereby enhancing safety and efficiency of lithium production. This necessitates a combination of innovative membrane technologies and effective dehydration strategies, which are crucial to developing efficient and safe methods for lithium extraction from brine. Despite efforts to tackle this issue, there remains an unmet need to overcome inherent limitations. SUMMARY

[0003] Electrodeposition, a process wherein lithium metal is directly formed on an electrode by passing a current through a lithium-rich solution like brine or electrolyte, is crucial for generating lithium for next-generation battery anodes. Despite lithium metal's potential, due to its high theoretical capacity and the lowest electrochemical potential among known elements, the electrodeposition process faces challenges. These include the formation of dendritic structures and side reactions with electrolytes that pose safety concerns.

[0004] One specific challenge arises from the water content in brine used for lithium electrodeposition. Lithium can react with water to form lithium hydroxide and hydrogen, leading to wasteful reactions and potential safety hazards due to the production of flammable hydrogen gas. Even without direct reactions, water can still impact the electrodeposition process by causing the formation of a solid-electrolyte interphase (SEI) layer on the lithium electrode. Although this layer prevents direct contact between lithium and the electrolyte, thereby reducing side reactions, it can become unstable over time, causing a loss of efficiency. To address theseAtty Dkt No.: 65848-720601 issues, a significant strategy employed is dehydration, which can be implemented in the flow line to the deposition cell or within the cell itself. Dehydration in the flow line can involve heating the electrolyte to evaporate the water or using a desiccant. Alternatively, in the deposition cell, dehydration may be achieved using hydrophobic membranes or electrolytes that repel water, preventing it from reaching the lithium electrode. Such methods allow for the separation and removal of water from the system, enhancing the electrodeposition process's safety and efficiency. In some aspects, the present disclosure provides a flexible conductive composite membrane comprising: a hydrophobic film layer and one or more lithium ion conductive particles, wherein the composite membrane is substantially impermeable to water and is configured to provide a Li+conductivity of at least about 1.0 × 10-6S / cm through the composite membrane.

[0005] In some embodiments, the composite membrane has a Young’s modulus of less than about 10 GPa. In some embodiments, the composite membrane has a water permeability of less than about 1.0 g / m2･day under 1 mA / cm2of the current density as measured at least in part by Near-Infrared (NIR) spectroscopy. In some embodiments, the composite membrane has a water permeability of less than about 10-10m2s-1Pa-1, 10-15m2s-1Pa-1, 10-18m2s-1Pa-1, or 10-21m2s-1Pa-1under 1 mA / cm2of the current density as measured at least in part by Near-Infrared (NIR) spectroscopy. In some embodiments, the composite membrane has a water permeability of less than about 10-21m2s-1Pa-1under 1 mA / cm2of the current density as measured at least in part by Near-Infrared (NIR) spectroscopy. In some embodiments, the composite membrane comprises less than about 0.01% pores by volume. In some embodiments, the composite membrane is bendable to a radius of curvature of at least about 1 mm without substantially affecting the water impermeability and / or the Li+conductivity of the composite membrane.

[0006] In some embodiments, the one or more lithium ion conductive particles comprise a particle density of at least about 30%. In some embodiments, the one or more lithium ion conducting particles selectively conducts lithium ions. In some embodiments, a transference number of lithium ions in the one or more lithium ion conducting particles is between 0.90 and 1. In some embodiments, the one or more lithium ion conductive particles comprises a ceramic material. In some embodiments, the ceramic material comprises lithium ion conductive glass ceramic (LICGC), lithium aluminum titanium phosphate (LATP), lithium lanthanum zirconium tantalum oxide (LLZTO), lithium lanthanum zirconium aluminum oxide (LLZAO), LiFePO4, LiCoO2, lithium-lanthanum titanates (LLTO), garnet type electrolytes, NASICON, LISICON and Thio-LISICON electrolytes, Li7La3Zr3O12 (LLZO), cubic phase LLZO, LATP, and any combination thereof. In some embodiments, the one or more lithium ion conducting particlesAtty Dkt No.: 65848-720601 comprise a hydrophobically modified surface. In some embodiments, the one or more lithium ion conducting particles comprise a size of at least 20 μm. In some embodiments, the one or more lithium ion conducting particles each provide an exposed particle surface on two sides of the hydrophobic film layer.

[0007] In some embodiments, at least one side of the composite membrane comprises a lithium conductive polymer. In some embodiments, the lithium conductive polymer comprises a block copolymer. In some embodiments, a portion of the block copolymer is in contact with lithium metal, wherein the portion is substantially unreactive with the lithium metal.

[0008] In some embodiments, the composite membrane comprises a thermoplastic polymer or a thermoset polymer. In some embodiments, the lithium conductive polymer comprises an apparent melting transition temperature greater than 20 °C. In some embodiments, ion conductive domains of the lithium conductive polymer comprise a glass transition temperature of less than 20 °C. In some embodiments, the lithium conductive polymer increases uniformity of current distribution for lithium plating. In some embodiments, the lithium conductive polymer substantially prevents or inhibits reactions between plated lithium and ceramic particle.

[0009] In some embodiments, the one or more lithium ion conductive particles comprises an adhesive configured to adhere or bind to the hydrophobic film layer. In some embodiments, the adhesive comprises one or more compatibilizing small molecules that are coupled to the one or more lithium conductive particles. In some embodiments, the adhesive comprises one or more compatibilizing oligomer molecules that are coupled to the one or more lithium conductive particles. In some embodiments, the adhesive comprises one or more compatibilizing polymer molecules that are coupled to the one or more lithium conductive particles. In some embodiments, the adhesive is miscible in the hydrophobic film layer. In some embodiments, the adhesive forms a physical bond with the hydrophobic film layer. In some embodiments, the adhesive forms a chemical bond with the hydrophobic film layer. In some embodiments, the one or more compatibilizing polymer or oligomer molecules are configured to repel the one or more lithium conductive particles from one another to reduce particle-particle contact between the one or more lithium conductive particles. In some embodiments, the one or more lithium conductive particles each comprises at least a distribution of the one or more compatibilizing polymer molecules around the one or more lithium conductive particles.

[0010] In some aspects, the present disclosure provides a rechargeable energy source system comprising: a composite membrane comprising a hydrophobic film layer and one or more lithium ion conductive particles, wherein the one or more lithium ion conducting particles each provide an exposed particle surface on two sides of the hydrophobic film layer, wherein theAtty Dkt No.: 65848-720601 composite membrane is substantially impermeable to water when the rechargeable energy source system is in operation or not in operation.

[0011] In some embodiments, the composite membrane is substantially impermeable to water over at least 100 charge-discharge cycles of the rechargeable energy source system. In some embodiments, the rechargeable energy source system further comprises a polymer layer between a lithium metal anode and the composite membrane. In some embodiments, the polymer layer is configured to prevent the one or more lithium ion conductive particles in the composite membrane from contacting the lithium metal anode.

[0012] In some embodiments, the system further comprises a porous filter between a lithium metal anode and the composite membrane. In some embodiments, the porous filter is configured to prevent the one or more lithium ion conductive particles in the composite membrane from contacting the lithium metal anode. In some embodiments, the porous filter is wet with a liquid organic electrolyte.

[0013] In some embodiments, the rechargeable energy source system comprises an anodeless system. In some embodiments, the rechargeable energy source system comprises a lithium metal layer having a thickness greater than 10 μm when the rechargeable energy source system is fully charged.

[0014] In some embodiments, the composite membrane is flexible. In some embodiments, the composite membrane has a Young’s modulus less than about 10 GPa.

[0015] In some embodiments, the rechargeable energy source system has a curved form factor.

[0016] In some aspects, the present disclosure provides a method of operating a rechargeable energy source system, comprising: depositing lithium from a cathode at an anode through a composite membrane comprising a hydrophobic film layer and one or more lithium ion conductive particles, wherein the one or more lithium ion conducting particles each provide an exposed particle surface on two sides of the hydrophobic film layer, wherein the depositing of the lithium at the anode is substantially free of side reactions caused by water and / or other impurities.

[0017] In some embodiments, the rechargeable energy source system comprises an aqueous electrolyte between the cathode and the composite membrane. In some embodiments, the rechargeable energy source system comprises a non-aqueous electrolyte between the cathode and the composite membrane. In some embodiments, the rechargeable energy source system comprises a non-aqueous electrolyte between the anode and the composite membrane. In some embodiments, the depositing lithium is performed using at least in part a current density of at least about 1 mA / cm2.Atty Dkt No.: 65848-720601

[0018] In some embodiments, the other impurities comprise oxygen, an organic electrolyte, a surfactant, sodium, potassium, magnesium, calcium, boron, chlorine, SO4, nitrogen, an alkali metal, an alkali earth metal, or any combination thereof.

[0019] In some aspects, the present disclosure provides a system for lithium extraction from brine comprising: a composite membrane comprising a hydrophobic film layer and one or more lithium ion conductive particles, wherein the composite membrane is substantially impermeable to water when the system for lithium extraction is in operation or not in operation.

[0020] In some embodiments, the composite membrane is substantially impermeable to water over at least 100 lithium plating or deposition-stripping cycles of the system for lithium extraction.

[0021] In some embodiments, the system further comprises a polymer layer between a lithium metal anode and the composite membrane. In some embodiments, the polymer layer is configured to prevent the one or more lithium ion conductive particles in the composite membrane from contacting the lithium metal anode.

[0022] In some embodiments, the system further comprises a porous filter between a lithium metal anode and the composite membrane. In some embodiments, the porous filter is configured to prevent the one or more lithium ion conductive particles in the composite membrane from contacting the lithium metal anode. In some embodiments, the porous filter is wet with a liquid organic electrolyte.

[0023] In some embodiments, the composite membrane is flexible. In some embodiments, the composite membrane has a Young’s modulus less than about 10 GPa. In some embodiments, the composite membrane has a curved form factor.

[0024] In some aspects, the present disclosure provides a method of operating a system for lithium extraction from brine, comprising: depositing lithium from a lithium metal anode at a cathode through a composite membrane comprising a hydrophobic film layer and one or more lithium ion conductive particles, wherein the depositing of the lithium at the cathode is substantially free of side reactions caused by water and / or other impurities.

[0025] In some embodiments, the depositing lithium is performed using at least in part a current density of at least about 1 mA / cm2.

[0026] In some embodiments, the other impurities comprise oxygen, an organic electrolyte, a surfactant, sodium, potassium, magnesium, calcium, boron, chlorine, SO4, nitrogen, an alkali metal, an alkali earth metal, or any combination thereof.

[0027] In some embodiments, a system for extracting lithium metal from a brine can comprise an anode, disposed in the lithium resource, and a solution of an organic solvent having asAtty Dkt No.: 65848-720601 dissolved solutes a coordination compound, and a lithium salt, wherein the solution is in contact with the lithium resource. In some embodiments, the organic solvent is insoluble in the lithium resource. In some embodiments, the coordination compound and the lithium salt are also insoluble in the lithium resource, and the coordination compound selectively coordinates lithium cation in preference to other cations. In some embodiments, water is insoluble in the organic solvent. As used herein, “insoluble” may be used to refer to describe the compatibility of two substances where the two substances phase separate when in contact with each other. Small amounts of one substance forming one phase may solvate in the other phase. The organic solvent may be insoluble in the lithium resource to the extent that organic solvent retains a substantial portion of its mass upon multiple instances of contact with the lithium resource. For example, less than 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, or 0.01% of the mass of the organic solvent may dissolve in the lithium resource. The lithium resource may be insoluble in the organic solvent to the extent that negligible amounts of water from the lithium resource may solvate in the organic solvent. For example, the negligible amount of water may be less than 10000, 1000, 100, 10, or 1 ppm, such that the presence of water in the organic solvent does not substantially affect the quality of lithium metal deposited using the system. Some embodiments can further comprise an electrode which is in contact with the water-immiscible phase but physically separated from the lithium resource. The system can be configured so that when voltage is applied across the anode and the electrically conductive substrate, lithium cation is extracted from the lithium resource and a layer of lithium metal or lithium metal alloy is deposited on the surface of the electrode.

[0028] In some embodiments, a coordination compound can be a clathrate, a crown ether, or a cryptand. Clathrates can be coordination compounds that form molecular “cages” that can envelop and bind a target chemical entity, often with a high degree of specificity. Crown ethers can comprise cyclic compounds containing several ether groups. Cryptands can be polycyclic compounds that provide an additional class of alkali and alkaline earth cation selective clathrates, and can comprise nitrogen containing cryptands and orthoester cryptands.

[0029] In some embodiments, the coordination compound is a lithium ion selective clathrate. In some embodiments, the lithium ion selective clathrate is selected from the group consisting of a crown ether, a nitrogen-containing cryptand, and an orthoester cryptand. In some embodiments, the clathrate is a crown ether. In some embodiments, the crown ether is selected from the group consisting of 14-crown-4, substituted derivatives of 14-crown-4, 12-crown-4, substituted derivatives of 12-crown-4, 15-crown-5, substituted derivatives of 15-crown-5, and combinations thereof.Atty Dkt No.: 65848-720601

[0030] In some embodiments, the cryptand is selected from the group consisting of cryptand X.Y.Z. (X=1-10, Y=1-10, Z=1-10) and combinations thereof. In some embodiments, the crown ether or cryptand may be functionalized by a functional group including, but not being limited to fluoroalkyl, azide, amide, and the like. The term "functionalized crown ethers and cryptands" refers to the cage molecules to which some functional groups (e.g., fluoroalkyl, azide, amide, etc) are attached.

[0031] The lithium ion selective clathrate may selectively bind to a lithium ion over other cations present in the lithium resource, e.g., magnesium, calcium, sodium, or potassium. The degree of selectivity may depend on the operating conditions, e.g., the temperature, the pressure, and the specific composition of the lithium resource and the organic solvent.

[0032] In some embodiments, the lithium salt comprises an anion with the chemical structure of (RS(O)2)2N-, where R is a substituent selected from the group of alkyl, perfluorinated alkyl, partially fluorinated alkyl, aryl, perfluorinated aryl, partially fluorinated aryl, and combinations thereof. In some embodiments, R can comprise a polymer. For example, R can be a polymer backbone comprising a plurality of anionic moieties that balance the positive charge of lithium ions. A lithium salt can comprise lithium bis(oxalato)borate, lithium 12-hydroxystearate, lithium acetate, lithium amide, lithium aspartate, lithium azide, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium borohydride, lithium bromide, lithium carbonate, lithium chlorate, lithium chloride, lithium citrate, lithium cyanide, lithium diphenylphosphide, lithium hexafluorogermanate, lithium hexafluorophosphate, lithium hypochlorite, lithium hypofluorite, lithium metaborate, lithium methoxide, lithium naphthalene, lithium niobate, lithium nitrate, lithium nitrite, lithium oxalate, lithium perchlorate, lithium stearate, lithium succinate, lithium sulfate, lithium sulfide, lithium superoxide, lithium tantalate, lithium tetrachloroaluminate, lithium tetrafluoroborate, lithium tetrakis(pentafluorophenyl)borate, lithium triflate, lithium tungstate, or any combination thereof. In some embodiments, a lithium salt can comprise an organic anion selected from the group consisting of bis(trifluoromethanesulfonyl)imide (TFSI), and any combination thereof. In some embodiments, a lithium salt comprises ionic liquid selected from the group consisting of N- butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PyrTFSI), or l-ethyl-3- methylimidazolium-bis(trifluoromethylsulfonyl)imide (EMI-TFSI), any combination thereof. In some embodiments, a lithium salt can comprise Li2SO4, Li2CO3, LiPF6, LiBF4, LiClO4, LiTFSI, and combinations thereof. In some embodiments, a lithium salt can comprise LiPF6, LiBF4, LiSbF6, LiAsF6, LiSbF6, LiCF3SO3, Li(CF3SO2)3C, Li(CF3SO2)2N, LiC4F9SO3, LiClO4, LiAlO4, LiAlCl4, LiAlF4, LiBPh4, LiBioCl10, CH3SO3Li, C4F3SO3Li, (CF3SO2)2NLi,Atty Dkt No.: 65848-720601 LiN(CxF2x+1SO2)(CxF2y+1SO2) (wherein x and y are natural numbers), CF3CO2Li, LiCl, LiBr, LiI, LiBOB (lithium bis(oxalato)borate), lower aliphatic carboxylic acid lithium, lithium terphenylborate, lithium imide, or any combination thereof. In some embodiments, a concentration of the lithium salt may be in a range of about 0.1 molar (“M”) to about 2.0 M. In some embodiments, a concentration of the lithium salt is at least 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, or 3 M. In some embodiments, a concentration of the lithium salt is at most 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 7.0, 8.0, 9.0, 10, 12, 14, 16, 18, 20, 22, 24, or 25 M.

[0033] In some embodiments, the organic solvent is selected from the group consisting of CH3(CH2)pO[(CH2)qOCH2(CF2)nCH2O]x(CH2)rCH3(n = 1-15, p = 0-15, q = 0-15, r = 0-15, x = 1-30), CH3[(CH2)pOCH2(CF2)nCH2O(CH2)q]xCH3 (n = 1-15, p = 0-15, q = 0-15, x = 1-30, wherein the n, p, and x is independent from the values of n, p, and x chosen in the prior chemical structure), alkanes, and combinations thereof.

[0034] In some embodiments, the organic solvent comprises CH3(CH2)pO[(CH2)qOCH2(CF2)nCH2O]x(CH2)rCH3, wherein n is at least 1, 5, 10, or 15. In some embodiments, the organic solvent comprises CH3(CH2)pO[(CH2)qOCH2(CF2)nCH2O]x(CH2)rCH3, wherein n is at most 1, 5, 10, or 15. In some embodiments, the organic solvent comprises CH3(CH2)pO[(CH2)qOCH2(CF2)nCH2O]x(CH2)rCH3, wherein p is at least 1, 5, 10, or 15. In some embodiments, the organic solvent comprises CH3(CH2)pO[(CH2)qOCH2(CF2)nCH2O]x(CH2)rCH3, wherein p is at most 1, 5, 10, or 15. In some embodiments, the organic solvent comprises CH3(CH2)pO[(CH2)qOCH2(CF2)nCH2O]x(CH2)rCH3, wherein q is at least 1, 5, 10, or 15. In some embodiments, the organic solvent comprises CH3(CH2)pO[(CH2)qOCH2(CF2)nCH2O]x(CH2)rCH3, wherein q is at most 1, 5, 10, or 15. In some embodiments, the organic solvent comprises CH3(CH2)pO[(CH2)qOCH2(CF2)nCH2O]x(CH2)rCH3, wherein r is at least 1, 5, 10, or 15. In some embodiments, the organic solvent comprises CH3(CH2)pO[(CH2)qOCH2(CF2)nCH2O]x(CH2)rCH3, wherein r is at most 1, 5, 10, or 15. In some embodiments, the organic solvent comprises CH3(CH2)pO[(CH2)qOCH2(CF2)nCH2O]x(CH2)rCH3, wherein x is at least 1, 5, 10, 15, 20, 25, or 30. In some embodiments, the organic solvent comprises CH3(CH2)pO[(CH2)qOCH2(CF2)nCH2O]x(CH2)rCH3, wherein x is at most 1, 5, 10, 15, 20, 25, or 30.

[0035] In some embodiments, the organic solvent comprises CH3[(CH2)pOCH2(CF2)nCH2O(CH2)q]xCH3, wherein n is at least 1, 5, 10, or 15. In some embodiments, the organic solvent comprises CH3[(CH2)pOCH2(CF2)nCH2O(CH2)q]xCH3,Atty Dkt No.: 65848-720601 wherein n is at most 1, 5, 10, or 15. In some embodiments, the organic solvent comprises CH3[(CH2)pOCH2(CF2)nCH2O(CH2)q]xCH3, wherein p is at least 1, 5, 10, or 15. In some embodiments, the organic solvent comprises CH3[(CH2)pOCH2(CF2)nCH2O(CH2)q]xCH3, wherein p is at most 1, 5, 10, or 15. In some embodiments, the organic solvent comprises CH3[(CH2)pOCH2(CF2)nCH2O(CH2)q]xCH3, wherein q is at least 1, 5, 10, or 15. In some embodiments, the organic solvent comprises CH3[(CH2)pOCH2(CF2)nCH2O(CH2)q]xCH3, wherein q is at most 1, 5, 10, or 15. In some embodiments, the organic solvent comprises CH3[(CH2)pOCH2(CF2)nCH2O(CH2)q]xCH3, wherein x is at least 1, 5, 10, 15, 20, 25, or 30. In some embodiments, the organic solvent comprises CH3[(CH2)pOCH2(CF2)nCH2O(CH2)q]xCH3, wherein x is at most 1, 5, 10, 15, 20, 25, or 30.

[0036] In some embodiments, the organic solvent comprises an ether functional group, a fluoroalkyl group, a fluoroether group, or any combination thereof. In some embodiments, an organic solvent can comprise 1,3-dioxolane (DOL), 1,2-dimethoxyethane, dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, 1,3-dioxolan- 2-one, 4-methyl-1,3-dioxolan-2-one, oxolan-2-one, dimethoxyethane, bis(2,2,2-trifluoroethyl) ether, poly(ethylene glycol), perfluorinated poly(ethylene glycol), partially fluorinated poly(ethylene glycol), 2,2,3,3-tetrafluoropropyl trifluoromethyl ether, or any combination thereof. In some embodiments, an organic solvent can comprise an organic carbonate compound, an ester compound, an ether compound, a ketone compound, an alcohol compound, an aprotic bipolar solvent, a polar aprotic solvent, or a combination thereof. The carbonate compound can comprise an open chain carbonate compound, a cyclic carbonate compound, a fluorocarbonate derivative thereof, or a combination thereof. In some embodiments, the chain carbonate compound can comprise diethyl carbonate (“DEC”), dimethyl carbonate (“DMC”), dipropyl carbonate (“DPC”), methylpropyl carbonate (“MPC”), ethylpropylcarbonate (“EPC”), methylethyl carbonate (“MEC”), or a combination thereof. In some embodiments, the cyclic carbonate compound can comprise ethylene carbonate (“EC”), propylenecarbonate (“PC”), butylene carbonate (“BC”), fluoroethylene carbonate (“FEC”), vinylethylene carbonate (“VEC”), or a combination thereof. In some embodiments, the fluorocarbonate compound can comprise fluoroethylene carbonate (“FEC”), 4,5-difluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,4,5-trifluoroethylene carbonate, 4,4,5,5-tetrafluoroethylene carbonate, 4-fluoro-5- methylethylene carbonate, 4-fluoro-4-methylethylene carbonate, 4,5-difluoro-4-methylethylene carbonate, 4,4,5-trifluoro-5-methylethylene carbonate, trifluoromethylethylene carbonate, or a combination thereof. In some embodiments, the carbonate compound can comprise a combination of cyclic carbonate and chain carbonate, in consideration of the dielectric constantAtty Dkt No.: 65848-720601 and the viscosity of the electrolyte. In some embodiments, the carbonate compound can comprise a mixture of such chain carbonate and / or cyclic carbonate compounds as described above with a fluorocarbonate compound. In some embodiments, the fluorocarbonate compound may increase solubility of a lithium salt to improve ionic conductivity of the electrolyte, and may facilitate formation of the thin film on the anode with high Coulombic efficiency. In some embodiments, the ester compound comprises methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate (“MP”), ethyl propionate, γ-butyrolactone, decanolide, valerolactone, mevalonolactone, caprolactone, methyl formate, or any combination thereof. In some embodiments, the ether compound comprises dibutyl ether, tetraglyme, diglyme, 1,2- dimethoxyethane, 1,2-diethoxyethane, ethoxymethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, or any combination thereof. An example of the ketone compound is cyclohexanone. In some embodiments, the alcohol compound can comprise ethyl alcohol or isopropyl alcohol. In some embodiments, the aprotic solvent can comprise a nitrile (such as R— CN, wherein R is a C2-C20linear, branched, or cyclic hydrocarbon-based moiety that may comprise a double-bond, an aromatic ring or an ether bond), amides (such as formamide and dimethylformamide), dioxolanes (such as 1,2-dioxolane and 1,3-dioxolane), methylsulfoxide, sulfolanes (such as sulfolane and methylsulfolane), 1,3-dimethyl-2-imidazolidinone, N-methyl- 2-pyrrolidinone, nitromethane, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, triester phosphate, or any combination thereof. In some embodiments, an electrolyte can comprise an aromatic hydrocarbon organic solvent in a carbonate solvent. In some embodiments, an aromatic hydrocarbon organic solvent can comprise benzene, fluorobenzene, 1,2- difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene, 1,2,4- trifluorobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4- dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, iodobenzene, 1,2- diiodobenzene, 1,3-diiodobenzene, 1,4-diiodobenzene, 1,2,3-triiodobenzene, 1,2,4- triiodobenzene, 2-fluorotoluene, 3-fluorotoluene, 4-fluorotoluene, 2,3-difluorotoluene, 2,4- difluorotoluene, 2,5-difluorotoluene, 2,6-difluorotoluene, 3,4-difluorotoluene, 3,5- difluorotoluene, 2,3,4-trifluorotoluene, 2,3,5-trifluorotoluene, 2,3,6-trifluorotoluene, 3,4,5- trifluorotoluene, 2,4,5-trifluorotoluene, 2,4,6-trifluorotoluene, 2-chlorotoluene, 3-chlorotoluene, 4-chlorotoluene, 2,3-dichlorotoluene, 2,4-dichlorotoluene, 2,5-dichlorotoluene, 2,6- dichlorotoluene, 2,3,4-trichlorotoluene, 2,3,5-trichlorotoluene, 2,3,6-trichlorotoluene, 3,4,5- trichlorotoluene, 2,4,5-trichlorotoluene, 2,4,6-trichlorotoluene, 2-iodotoluene, 3-iodotoluene, 4- iodotoluene, 2,3-diiodotoluene, 2,4-diiodotoluene, 2,5-diiodotoluene, 2,6-diiodotoluene, 3,4- diiodotoluene, 3,5-diiodotoluene, 2,3,4-triiodotoluene, 2,3,5-triiodotoluene, 2,3,6-triiodotoluene,Atty Dkt No.: 65848-720601 3,4,5-triiodotoluene, 2,4,5-triiodotoluene, 2,4,6-triiodotoluene, o-xylene, m-xylene, p-xylene, and combinations thereof.

[0037] In some embodiments, a method for extracting lithium metal from a lithium resource can comprise disposing an anode in the lithium resource. In some embodiments, the method can comprise placing a solution in contact with the lithium resource. The solution can comprise an organic solvent. The solution can comprise a coordination compound and a lithium salt. In some embodiments, the organic solvent is substantially insoluble in the lithium resource. In some embodiments, the coordination compound selectively coordinates lithium cation in preference to other cations. In some embodiments, the method can comprise disposing an electrode to be in contact with the solution. The electrode can be physically separated from the lithium resource. In some embodiments, the method can comprise applying voltage across the anode and the electrode. A layer of lithium metal or lithium metal alloy can be deposited on a surface of the electrode.

[0038] In some embodiments, the method can comprise removing the layer of lithium metal or lithium metal alloy from contact with the lithium resource. In some embodiments, the method can comprise cleaning a surface of the layer of lithium metal or lithium metal alloy. The cleaning can be performed by contacting the surface with an organic solvent. The organic solvent can be, e.g., hexane, dimethyl carbonate or 1,2-dimethoxyethane. The contacting the organic solvent can be performed by soaking, rinsing, or both. In some embodiments, the cleaning comprises brushing with a soft sponge and / or sonication in the organic solvent.

[0039] In some embodiments, a system for extracting one or more metals from a brine comprises an anode. The anode can be disposed in the brine. The system can comprise an organic solution of an organic solvent having as dissolved solutes one or more coordination compounds, and salts of one or more metals. The organic solution can be in contact with the lithium resource. In some embodiments, the organic solvent, the one or more coordination compounds, and the coordination compounds are configured to coordinate cations of the one or more metals. Some embodiments further comprise an electrode, in contact with the solution. The electrode can be physically separated from the lithium resource. The system can be configured so that when voltage is applied across the anode and the electrode, cations of the one or more metals are extracted from the brine and a layer of a metal or metal alloy is deposited on a surface of the electrode.

[0040] In some embodiments, a coordination compound can be configured to selectively coordinate specific metal cations, thereby providing a means of controlling the composition of the layer of metal or metal alloy.Atty Dkt No.: 65848-720601

[0041] In some embodiments, a method for extracting lithium from a lithium resource comprises transporting lithium ions from the lithium resource to a non-aqueous electrolyte comprising one or more coordination compounds. The one or more coordination compounds can be configured to coordinate with the lithium ions. The method can comprise transporting the lithium ions coordinated by the one or more coordination compounds from the non-aqueous electrolyte to a substrate. The method can comprise electrodepositing lithium metal on the substrate by reducing the lithium ions to the lithium metal. In some embodiments, the transporting and the electrodepositing are performed concurrently. In some embodiments, the transporting and the electrodepositing are performed by applying an electric potential to one or more electrochemical cells, wherein the one or more electrochemical cells comprise or are in contact with the lithium resource, the non-aqueous electrolyte and the substrate.

[0042] In some embodiments, the one or more coordination compounds are substantially insoluble in the lithium resource. In some embodiments, water in the lithium resource is insoluble in the non-aqueous electrolyte. In some embodiments, the non-aqueous electrolyte comprises an organic solvent. In some embodiments, the organic solvent comprises a molecule comprising one or more carbon-fluorine bonds.

[0043] In some embodiments, the non-aqueous electrolyte comprises a lithium salt. In some embodiments, the lithium salt is substantially insoluble in the organic solvent in the absence of the one or more coordination compounds.

[0044] In some embodiments, the lithium resource comprises sodium, potassium, magnesium, calcium, boron, chlorine, SO42-, nitrogen, an alkali metal, an alkali earth metal, or any combination thereof. In some embodiments, the one or more coordination compounds selectively coordinate with the lithium ions. In some embodiments, the one or more coordination compounds preferentially coordinate with the lithium ions over non-lithium cations. In some embodiments, the non-lithium cations comprise any one of sodium, potassium, magnesium, calcium, and any combination thereof.

[0045] In some embodiments, the one or more coordination compounds comprise a plurality of ether groups, wherein oxygen atoms of the plurality of ether groups coordinate with the lithium ions. In some embodiments, the one or more coordination compounds comprise one or more crown ethers. In some embodiments, the one or more coordination compounds comprise a plurality of amine groups, wherein nitrogen atoms of the plurality of amine groups coordinate with the lithium ions. In some embodiments, the one or more coordination compounds comprise one or more cryptands. In some embodiments, the one or more coordination compoundsAtty Dkt No.: 65848-720601 comprise any one of lariat ethers, multi-armed ethers, calixarenes, spherands, cryptaspherand, hemispherand, podand, and any combination thereof.

[0046] In some embodiments, the lithium resource comprises a geological resource. In some embodiments, the lithium resource is aqueous. In some embodiments, the lithium resource comprises brine. In some embodiments, the lithium resource is pretreated by dilution, concentration, filtration, nanofiltration, absorption or extraction using organic molecules or inorganic sorbents, electrodialysis using a membrane, concentration and precipitation, solvent extraction, pH adjustment, or any combination thereof. In some embodiments, the pH adjustment comprises adding an acid, a base, a buffer, or any combination thereof. The pH can be adjusted to at least 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14. The pH can be adjusted to at most 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14. In some embodiments, the pretreatment removes magnesium in the aqueous lithium resource. In some embodiments, a ratio of magnesium to lithium in the aqueous lithium resource is about 0-100 by mass or by mols. The ratio of magnesium to lithium can be at least 0.001, 0.01, 0.1, 1, 10, 100, or 1000 by mass or by mols. The ratio of magnesium to lithium can be at most 0.001, 0.01, 0.1, 1, 10, 100, or 1000 by mass or by mols.

[0047] In some embodiments, the substrate comprises copper. In some embodiments, the lithium metal comprises less than 0.1 wt% or atomic% (at%) of nitrogen, oxygen, or both. In some embodiments, the lithium metal comprises less than 0.1 wt% or at% of boron. In some embodiments, the lithium metal comprises less than 0.1 wt% or at% of magnesium, aluminum, or both. In some embodiments, the lithium metal comprises less than 0.1 wt% or at% of non- conductive impurities. In some embodiments, the lithium metal comprises less than 0.1 wt% of lithium alloys. In some embodiments, the lithium metal comprises less than 1 non-lithium subsurface structure per mm3. In some embodiments, the lithium metal comprises less than 1 non-lithium crystalline subsurface structure per mm3. In some embodiments, the lithium metal comprises a thickness of less than 100 μm.

[0048] In some embodiments, a cathode can comprise copper, aluminum, graphite coated copper, nickel, silicon, silver, carbon (e.g., rough-surface carbon, graphene), a lithophilic material, aluminum, gold, a copper alloy (Cu-Zn, Cu-Al, Cu-Sn), or any combination thereof. The anode can comprise a layer of lithium metal deposited thereon. Lithium metal can be deposited on the negative electrode with a thickness of at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 μm. Lithium metal can be deposited on the negative electrode with a thickness of at least about 1, 5, 10, 20, 30, 40, 50, 100, 200, 300, 400, or 500 μm. Lithium metal can be deposited on the anode with a thickness of at most about 1, 5, 10, 20, 30, 40, 50, 100, 200, 300, 400, or 500 μm.Atty Dkt No.: 65848-720601 Lithium metal can comprise a thickness between 1 and 380 μm, between 1 and 370 μm, between 1 and 360 μm, between 1 and 350 μm, between 1 and 340 μm, between 1 and 330 μm, between 1 and 320 μm, between 1 and 310 μm, between 1 and 300 μm, between 1 and 250 μm, between 1 and 200 μm, between 1 and 150 μm, between 1 and 100 μm, between 1 and 90 μm, between 1 and 80 μm, between 1 and 70 μm, between 1 and 60 μm, between 1 and 50 μm, between 1 and 45 μm, between 1 and 40 μm, between 1 and 35 μm, between 1 and 30 μm, between 1 and 25 μm, between 1 and 20 μm, between 1 and 15 μm, between 1 and 10 μm, or between 1 and 5 μm.

[0049] In some aspects, the present disclosure provides a method for electrochemically extracting lithium from a lithium resource, comprising: (a) contacting an electrochemical cell with the lithium resource, wherein the electrochemical cell comprises an electrolyte, and the lithium resource comprises water; (b) depositing lithium on an electrode of the electrochemical cell by applying a voltage across the electrolyte; and (c) dehydrating the electrolyte to maintain water content in the electrolyte below a predetermined threshold.

[0050] In some embodiments, the dehydrating in (c) is performed separately from the depositing in (b). In some embodiments, the dehydrating in (c) occurs at a different location from the depositing in (b). In some embodiments, the dehydrating in (c) is performed in a chamber that is separated from a chamber performing the depositing in (b). In some embodiments, the dehydrating in (c) is performed in the same chamber as the depositing in (b).

[0051] In some embodiments, the dehydrating in (c) comprises evaporating and / or boiling water in the electrolyte. In some embodiments, the dehydrating in (c) comprises applying at least one of heat or vacuum to the electrolyte. In some embodiments, the dehydrating in (c) comprises bubbling gas through the electrolyte, wherein the gas comprises a temperature higher than the electrolyte. In some embodiments, the dehydrating in (c) comprises electrolyzing water in the electrolyte. In some embodiments, the dehydrating in (c) comprises contacting the electrolyte with an adsorbent or an absorbent to remove water from the electrolyte. In some embodiments, the adsorbent or the absorbent comprises a molecular sieve, aluminum oxide, zeolite, a metal- organic framework (MOF), copper benzene-1,3,5-tricarboxylate (CuBTC), or any combination thereof. In some embodiments, the predetermined threshold is 1000, 100, 50, or 10 ppm of water as determined using 1H NMR, Karl Fischer titration, or NIR spectroscopy. In some embodiments, the predetermined threshold is 100 ppm of water as determined using 1H NMR, Karl Fischer titration, or NIR spectroscopy. In some embodiments, the dehydrating in (c) removes at least 50, 60, 70, 80, 90, 95, 96, 97, 98, or 99% of the amount of water in the electrolyte as determined using 1H NMR, Karl Fischer titration, or NIR spectroscopy.Atty Dkt No.: 65848-720601

[0052] In some embodiments, the electrolyte is removed from the electrochemical cell prior to the dehydrating in (c). In some embodiments, the electrolyte is cycled through the electrochemical cell during the dehydrating in (c). In some embodiments, the electrolyte remains in the electrochemical cell prior to the dehydrating in (c). In some embodiments, the dehydrating in (c) is performed concurrently with the depositing in (b). In some embodiments, the dehydrating in (c) is performed in parallel with the depositing in (b). In some embodiments, the dehydrating in (c) is performed at a different time from the depositing in (b). In some embodiments, the dehydrating in (c) is performed prior to the depositing in (b). In some embodiments, the electrolyte is contacted with water before the dehydrating. In some embodiments, the dehydrating in (c) is performed after the depositing in (b).

[0053] In some embodiments, the method further comprises depositing the lithium on a second electrode of the electrochemical cell by applying a voltage between the Li deposition substrate and the counter electrode in the lithium resource.

[0054] In some embodiments, the electrode is in the electrolyte, and the counter electrode is in the lithium resource. In some embodiments, the voltage is applied between the electrode and the counter electrode.

[0055] In some embodiments, the lithium resource comprises sodium, potassium, magnesium, calcium, boron, chlorine, SO42-, nitrogen, an alkali metal, an alkali earth metal, or any combination thereof. In some embodiments, a ratio of magnesium to lithium in the lithium resource is about 0-1000. In some embodiments, the lithium resource comprises a geological resource. In some embodiments, the lithium resource comprises brine. In some embodiments, the lithium resource comprises an aqueous solution of metal salts comprising (i) a lithium salt and (ii) a sodium salt, a magnesium salt, a calcium salt, a potassium salt, or any combination thereof. In some embodiments, the magnesium salt comprises MgCl2. In some embodiments, the sodium salt comprises NaCl. In some embodiments, the lithium resource comprises LiCl, Li2SO4, or both. In some embodiments, the lithium resource is pretreated to remove a metal cation. In some embodiments, the metal cation comprises magnesium, calcium, sodium, potassium, iron, or any combination thereof. In some embodiments, the metal cation is removed by adsorption, extraction, absorption, electrodialysis, precipitation, nanofiltration, solvent extraction, or any combination thereof. In some embodiments, the adsorption or the extraction comprises binding the metal cation to a coordination compound. In some embodiments, the absorption is performed by contacting the lithium resource with lithium-manganese oxide, titanium oxide, aluminum hydroxide, iron phosphate, clay minerals, zeolite, zirconium phosphate, tin antimonate, antimony oxide, tantalum oxide, niobium oxide, or any combination thereof.Atty Dkt No.: 65848-720601

[0056] In some embodiments, the electrolyte comprises a non-volatile electrolyte. In some embodiments, the non-volatile electrolyte comprises a vapor pressure of less than 0.1, 0.01, or 0.001 hPa at 20 °C. In some embodiments, the electrolyte comprises a liquid electrolyte. In some embodiments, the electrolyte comprises a solid state electrolyte. In some embodiments, the electrolyte comprises a polymer. In some embodiments, the electrolyte comprises an oligomer. In some embodiments, the electrolyte comprises an ionic polymer. In some embodiments, the electrolyte comprises an ionic dopant. In some embodiments, the electrolyte comprises an ionic liquid. In some embodiments, the electrolyte comprises a deep eutectic solvent. In some embodiments, the electrolyte comprises a gel. In some embodiments, the gel is configured to substantially prevent convection in the electrolyte. In some embodiments, the gel is configured to substantially prevent diffusion of water to the electrode. In some embodiments, the gel is swollen with a non-volatile electrolyte. In some embodiments, the gel is self-healing. In some embodiments, the electrolyte comprises an elastomer. In some embodiments, the electrolyte comprises a lithium-ion selective polymer. In some embodiments, the electrolyte is a solid at room temperature. In some embodiments, the electrolyte is a liquid at operating temperatures, wherein the operating temperatures are above 30 °C. In some embodiments, the electrolyte comprises succinonitrile, malononitrile, glutaronitrile, adiponitrile, ethylene carbonate, propylene carbonate, diethyl carbonate, trimethylene carbonate, or any combination thereof.

[0057] In some embodiments, the lithium resource or the electrolyte comprises an additive, wherein the additive is configured to bind with lithium ions in the lithium resource preferentially over the lithium ions binding with water. In some embodiments, the additive forms molecular cages around lithium ions. In some embodiments, the additive comprises a coordination compound.

[0058] In some aspects, the present disclosure provides a system for electrochemically extracting lithium from a lithium resource, comprising: (a) an electrochemical cell comprising an electrolyte, wherein the electrochemical cell is configured to contact with the lithium resource; (b) a power source configured to apply a current across the electrolyte; and (c) a dehydrator configured to dehydrate the electrolyte to maintain water content in the electrolyte below a predetermined threshold.

[0059] In some embodiments, the system further comprises a vacuum, a heater, or both. In some embodiments, the system further comprises a channel or a chamber in (i) thermal communication with the heater, (ii) pneumatic communication with the vacuum, or (iii) both, wherein the chamber is configured to receive the electrolyte from the electrochemical cell. In some embodiments, the dehydrator comprises a column containing an adsorbent or an absorbentAtty Dkt No.: 65848-720601 configured to remove water from the electrolyte, wherein the column is configured to receive the electrolyte from the electrochemical cell. In some embodiments, the dehydrator comprises an electrode configured to electrolyze water in the electrolyte.

[0060] In some embodiments, the electrolyte comprises a non-volatile electrolyte. In some embodiments, the electrolyte comprises a gel. In some embodiments, the electrolyte comprises a coordination compound.

[0061] In some aspects, the present disclosure provides a lithium conductive membrane comprising: a. a polymer comprising a hydrophobic repeating unit and a coordination chemistry, and wherein the coordination chemistry is configured to coordinate with lithium ions; and b. the lithium ions; wherein the lithium conductive membrane is configured to provide a water permeability of less than 1.0 g / m2･day as measured at least in part by Near-Infrared (NIR) spectroscopy, and wherein the lithium conductive membrane is configured to provide a Li+ conductivity of at least about 1.0 × 10-6S / cm at room temperature through the lithium conductive membrane.

[0062] In some embodiments, the polymer is a copolymer. In some embodiments, the polymer is an alternating, random, graft, or block copolymer. In some embodiments, the hydrophobic repeating unit comprises: a. an acrylate monomer selected from the group consisting of: methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, lauryl acrylate, alkyl acrylate, and PDMS acrylate; b. a methacrylate monomer selected from the group consisting of: methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, alkyl acrylate, and PDMS acrylate; c. a siloxane monomer selected from the group consisting of dimethyl siloxane, and diethyl methoxy siloxane; d. a fluoroalkyl monomer selected from the group consisting of: a perfluoroalkyl monomer, a partially fluorinated monomer, octafluoropentyl acrylate, octafluoropentyl methacrylate, wherein the partially fluorinated monomer comprises an ester of acrylic acid (CH2CHCOOR) or methacrylic acid (CH2C(CH3)COOR), wherein R is selected from a group consisting of CHxFy, CH2CHxFy, (CH2CH2O)nCHxFy, CH2OCHxFy, CH2OCH2CHxFy, CH2OCHxFy, CH2OCH2CHxFy, (CH2CH2O)nCH2OCH2CHxFy, CH2(CF2)nCH2OCHxFy, CH2(CF2)nCH2OCH2OCHxFy, CH2(CF2)nCH2OCH2OCH2CHxFy, CH2(CF2)nCH2OCH2OCH2CH2OCH2CHxFy, and CH2(CF2)nCH2OCH2OCH2CH2OCHxFy((x,y) = (0, 3), (1, 2), (2, 1), or (3, 0), n = 0-15); e. an anionic monomer selected from the group consisting of: -(CF2)m-SO2-N--SO2-(CF2)n-CF3 (m = 0-5, n = 0-5), -(CF2)m-SO2-N--SO2-(CHF2)n- CHF2, -(CF2)m-SO2-N--SO2-(CF2)n-CH2F, -COO-, -SO3-, -cyano(trifluoromethanesulfonyl)imide, -2-trifluoromethyl-4,5-dicyanoimidazolide, wherein the anionic monomer is present in a ratio of about 1:1 with the coordination compound; f. a lithium-selective monomer selected from theAtty Dkt No.: 65848-720601 group consisting of 12-crown-4, 14-crown-4, 15-crown-5, cryptand [X.Y.Z] (X = 1-10, Y = 1- 10, Y = 1-10), substituted derivatives of 12-crown-4, substituted derivatives of 14-crown-4, substituted derivatives of 15-crown-5, substituted derivatives of cryptand [X.Y.Z], and combinations thereof; g. a lithium-selective monomer consisting of a crown ether having the chemical structure:whereinOis connected to acrylic group, methacrylic group, or any repeating unit of the polymer, and wherein R is a pendant organic group, which is chosen from the group consisting of -(CH2)mCH3and -(CF2)pCF3(m = 5-10 and p = 0-10), -CHxFy, -CH2CHxFy, - (CH2CH2O)nCHxFy, -CH2OCHxFy, -CH2OCH2CHxFy, -CH2OCHxFy,- CH2OCH2CHxFy, - (CH2CH2O)nCH2OCH2CHxFy, -CH2(CF2)nCH2OCHxFy, -CH2(CF2)nCH2OCH2OCHxFy, - CH2(CF2)nCH2OCH2OCH2CHxFy, -CH2(CF2)nCH2OCH2OCH2CH2OCH2CHxFy, and - CH2(CF2)nCH2OCH2OCH2CH2OCHxFy((x,y) = (0, 3), (1, 2), (2, 1), or (3, 0), n = 0-15); h. a norbornene monomer selected from any of the groups listed in a-g; i. a polyphosphazene-based branched polymer, wherein the branched polymer consists of any of the groups listed in a-g; j. a PDMS-based branched polymer where the branched molecules consisting of any of the groups listed in a-g; k. a blend of (A) polybutadiene, polyisoprene or poly(styrene-butadiene-styrene) and (B) lithium conductive polymer developed using any of the groups listed in a-j, wherein the blend film can be further modified by surface grafting of alkylthiols, perfluoroalkyl thiols, or thiols substituted by a substitute group selected from cryptand [X.Y.Z] (X = 1-10, Y = 1-10, Y = 1-10), 12-crown-4, 14-crown-4, 15-crown-5, -(CH2)mCH3 and -(CF2)pCF3 (m = 5-10 and p = 0- 10), -CHxFy, -CH2CHxFy, - (CH2CH2O)nCHxFy, -CH2OCHxFy, -CH2OCH2CHxFy, -CH2OCHxFy,- CH2OCH2CHxFy, -(CH2CH2O)nCH2OCH2CHxFy, -CH2(CF2)nCH2OCHxFy, - CH2(CF2)nCH2OCH2OCHxFy, -CH2(CF2)nCH2OCH2OCH2CHxFy, - CH2(CF2)nCH2OCH2OCH2CH2OCH2CHxFy, and -CH2(CF2)nCH2OCH2OCH2CH2OCHxFy ((x,y) = (0, 3), (1, 2), (2, 1), or (3, 0), n = 0-15).Atty Dkt No.: 65848-720601

[0063] In some embodiments, the polymer comprises an additive configured to increase the Li+conductivity. In some embodiments, the additive is hydrophilic. In some embodiments, the hydrophilic additive comprises polyethylene glycol methacrylate. In some embodiments, the polymer comprises a cross-linker. In some embodiments, the polymer is functionalized with the coordination compound in an amount sufficient to provide a percolating network of lithium ion conductive paths in the lithium conductive membrane. In some embodiments, the coordination compound is functionalized to the polymer via a vinyl, aldehyde, allylic, acrylate, amine, azide, alkyne, alkene, or thiol functional groups. In some embodiments, the coordination compound comprises a crown ether or a cryptand. In some aspects, the present disclosure provides a method comprising electrochemically extracting lithium ions from brine using the membrane disclosed herein.

[0064] In some aspects, the present disclosure provides a flexible conductive composite membrane comprising: a hydrophobic film layer and one or more lithium ion conductive particles, wherein the composite membrane is substantially impermeable to water and is configured to provide a Li+conductivity of at least about 1.0 × 10-5S / cm through the composite membrane.

[0065] In some embodiments, the composite membrane has a Young’s modulus of less than about 10 GPa. In some embodiments, the composite membrane has a water permeability of less than about 1.0 g / m2･day under 1 mA / cm2of the current density as measured at least in part by Near-Infrared (NIR) spectroscopy. In some embodiments, the composite membrane comprises less than about 0.01% pores by volume. In some embodiments, the composite membrane is bendable to a radius of curvature of at most about 1 mm without substantially affecting a water impermeability and / or the Li+conductivity of the composite membrane.

[0066] In some embodiments, the one or more lithium ion conductive particles comprise a particle density of at least about 30%. In some embodiments, the one or more lithium ion conducting particles selectively conducts lithium ions. In some embodiments, a transference number of lithium ions in the one or more lithium ion conducting particles is between 0.90 and 1. In some embodiments, the one or more lithium ion conductive particles comprises a ceramic material.

[0067] In some embodiments, the ceramic material comprises lithium ion conductive glass ceramic (LICGC), lithium aluminum titanium phosphate (LATP), lithium lanthanum zirconium tantalum oxide (LLZTO), LiFePO4, LiCoO2, lithium-lanthanum titanates (LLTO), garnet type electrolytes, NASICON, LISICON and Thio-LISICON electrolytes, Li7LaZr3O12 (LLZO), cubic phase LLZO, LATP, and any combination thereof.Atty Dkt No.: 65848-720601

[0068] In some embodiments, the one or more lithium ion conducting particles comprise a hydrophobically modified surface. In some embodiments, the one or more lithium ion conducting particles comprise a size of at least 20 μm. In some embodiments, the one or more lithium ion conducting particles each provide an exposed particle surface on two sides of the hydrophobic film layer.

[0069] In some embodiments, the composite comprises three layers comprising two hydrophobic layers and one hydrophilic layer, wherein the hydrophilic layer is between the two hydrophobic layers. In some embodiments, a layer of the two hydrophobic layers is adhered to the hydrophilic layer by an adhesive. In some embodiments, at least one side of the composite membrane comprises a lithium conductive polymer.

[0070] In some embodiments, the lithium conductive polymer comprises a block copolymer. In some embodiments, a portion of the block copolymer is in contact with lithium metal, wherein the portion is substantially unreactive with the lithium metal. In some embodiments, the composite membrane comprises a thermoplastic polymer or a thermoset polymer. In some embodiments, the lithium conductive polymer comprises an apparent melting transition temperature greater than 20 °C. In some embodiments, ion conductive domains of the lithium conductive polymer comprise a glass transition temperature of less than 20 °C.

[0071] In some embodiments, the lithium conductive polymer increases uniformity of current distribution for lithium plating. In some embodiments, the lithium conductive polymer substantially prevents or inhibits reactions between plated lithium and ceramic particle. In some embodiments, the one or more lithium ion conductive particles comprises an adhesive configured to adhere or bind to the hydrophobic film layer. In some embodiments, the adhesive comprises one or more compatibilizing small molecules that are coupled to the one or more lithium conductive particles. In some embodiments, the adhesive comprises one or more compatibilizing oligomer molecules that are coupled to the one or more lithium conductive particles. In some embodiments, the adhesive comprises one or more compatibilizing polymer molecules that are coupled to the one or more lithium conductive particles. In some embodiments, the adhesive is miscible in the hydrophobic film layer. In some embodiments, the adhesive forms a physical bond with the hydrophobic film layer. In some embodiments, the adhesive is forms a chemical bond with the hydrophobic film layer.

[0072] In some embodiments, the one or more compatibilizing polymer or oligomer molecules are configured to repel the one or more lithium conductive particles from one another to reduce particle-particle contact between the one or more lithium conductive particles. In some embodiments, the one or more lithium conductive particles each comprises at least a distributionAtty Dkt No.: 65848-720601 of the one or more compatibilizing polymer molecules around the one or more lithium conductive particles.

[0073] In some aspects, the present disclosure provides a rechargeable energy source system comprising: a composite membrane comprising a hydrophobic film layer and one or more lithium ion conductive particles, wherein the one or more lithium ion conducting particles each provide an exposed particle surface on two sides of the hydrophobic film layer, wherein the composite membrane is substantially impermeable to water when the rechargeable energy source system is in operation or not in operation.

[0074] In some embodiments, the composite membrane is substantially impermeable to water over at least 100 charge-discharge cycles of the rechargeable energy source system.

[0075] In some embodiments, the system further comprises a polymer layer between a lithium metal anode and the composite membrane. In some embodiments, the polymer layer is configured to prevent the one or more lithium ion conductive particles in the composite membrane from contacting the lithium metal anode. In some embodiments, the system further comprises a porous filter between a lithium metal anode and the composite membrane. In some embodiments, the porous filter is configured to prevent the one or more lithium ion conductive particles in the composite membrane from contacting the lithium metal anode. In some embodiments, the porous filter is wet with a liquid organic electrolyte.

[0076] In some embodiments, the rechargeable energy source system comprises an anodeless system. In some embodiments, the rechargeable energy source system comprises a lithium metal layer having a thickness greater than 10 μm when the rechargeable energy source system is fully charged.

[0077] In some embodiments, the composite membrane is flexible. In some embodiments, the composite membrane has a Young’s modulus less than about 10 GPa. In some embodiments, the rechargeable energy source system has a curved form factor.

[0078] In some aspects, the present disclosure provides a method of operating a rechargeable energy source system, comprising: depositing lithium from a cathode at an anode through a composite membrane comprising a hydrophobic film layer and one or more lithium ion conductive particles, wherein the one or more lithium ion conducting particles each provide an exposed particle surface on two sides of the hydrophobic film layer, wherein the depositing of the lithium at the anode is substantially free of side reactions caused by water and / or other impurities.

[0079] In some embodiments, the rechargeable energy source system comprises an aqueous electrolyte between the cathode and the composite membrane. In some embodiments,Atty Dkt No.: 65848-720601 rechargeable energy source system comprises a non-aqueous electrolyte between the cathode and the composite membrane. In some embodiments, the rechargeable energy source system comprises a non-aqueous electrolyte between the anode and the composite membrane.

[0080] In some embodiments, the depositing lithium is performed using at least in part a current density of at least about 1 mA / cm2.

[0081] In some embodiments, the other impurities comprise oxygen, an organic electrolyte, a surfactant, sodium, potassium, magnesium, calcium, boron, chlorine, SO42-, nitrogen, an alkali metal, an alkali earth metal, or any combination thereof.

[0082] In some aspects, the present disclosure provides a system for lithium extraction from brine comprising: a composite membrane comprising a hydrophobic film layer and one or more lithium ion conductive particles, wherein the composite membrane is substantially impermeable to water when the system for lithium extraction is in operation or not in operation.

[0083] In some embodiments, the composite membrane is substantially impermeable to water over at least 100 lithium plating or deposition-stripping cycles of the system for lithium extraction.

[0084] In some embodiments, the system further comprises a polymer layer between a lithium metal anode and the composite membrane. In some embodiments, the polymer layer is configured to prevent the one or more lithium ion conductive particles in the composite membrane from contacting the lithium metal anode. In some embodiments, the system further comprises a porous filter between a lithium metal anode and the composite membrane. In some embodiments, the porous filter is configured to prevent the one or more lithium ion conductive particles in the composite membrane from contacting the lithium metal anode. In some embodiments, the porous filter is wet with a liquid organic electrolyte.

[0085] In some embodiments, the composite membrane is flexible. In some embodiments, the composite membrane has a Young’s modulus less than about 10 GPa. In some embodiments, the composite membrane has a curved form factor.

[0086] In some aspects, the present disclosure provides a method of operating a system for lithium extraction from brine, comprising: depositing lithium from a lithium metal anode at a cathode through a composite membrane comprising a hydrophobic film layer and one or more lithium ion conductive particles, wherein the depositing of the lithium at the cathode is substantially free of side reactions caused by water and / or other impurities.

[0087] In some embodiments, the depositing lithium is performed using at least in part a current density of at least about 1 mA / cm2. In some embodiments, the other impurities comprise oxygen,Atty Dkt No.: 65848-720601 an organic electrolyte, a surfactant, sodium, potassium, magnesium, calcium, boron, chlorine, SO42-, nitrogen, an alkali metal, an alkali earth metal, or any combination thereof.

[0088] In some aspects, the present disclosure provides a computer program product comprising a computer-readable medium having computer-executable code encoded therein, the computer- executable code adapted to be executed to implement any one of the systems or methods disclosed herein.

[0089] In some aspects, the present disclosure provides a non-transitory computer-readable storage media encoded with a computer program including instructions executable by one or more processors to implement any one of the systems or methods disclosed herein.

[0090] In some aspects, the present disclosure provides a computer-implemented system comprising: a digital processing device comprising: at least one processor, an operating system configured to perform executable instructions, a memory, and a computer program including instructions executable by the digital processing device to perform any one of the systems or methods disclosed herein. INCORPORATION BY REFERENCE

[0091] All publications, patents, and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference. To the extent publications and patents or patent applications incorporated by reference contradict the disclosure contained in the specification, the specification is intended to supersede and / or take precedence over any such contradictory material. BRIEF DESCRIPTION OF THE DRAWINGS

[0092] The novel features of the disclosure are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present disclosure will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the disclosure are utilized, and the accompanying drawings of which:

[0093] FIG.1 shows a system for extracting lithium from a lithium resource.

[0094] FIGS.2A-2B show the types of water species that can be transported in a system for extracting lithium from a lithium resource.

[0095] FIG.3 shows the types of water species that can be transported in a system for extracting lithium from a lithium resource.Atty Dkt No.: 65848-720601

[0096] FIG.4A shows an illustration of an electrochemical experiment conducted to deposit lithium from a lithium resource.

[0097] FIG.4B provides an illustration of some strategies for dry electrodepositing lithium from a lithium resource.

[0098] FIGS.5A-5C show a schematic of a conductive composite membrane and its use in a system for extracting lithium from brine. FIG.5A shows a conductive composite membrane. FIG.5B shows a schematic of a conductive composite membrane that selectively conducts lithium ions. FIG.5C shows a system for extracting lithium from brine using a conductive composite membrane.

[0099] FIGS.6A-6B show a rechargeable energy source system comprising a conductive composite membrane.

[0100] FIG.7 shows a schematic of a solvent casting method for manufacturing a conductive composite membrane.

[0101] FIG.8 shows a schematic of a solvent casting method with annealing.

[0102] FIG.9 shows a schematic of a hot pressing method.

[0103] FIG.10 shows a schematic of a method of hot pressing lithium ion conductive particles into a polymer film.

[0104] FIGS.11A-11B show an arrangement of lithium ion conductive particles in a conductive composite membrane and its conductivity. FIG.11A shows an example of a hexagonal arrangement of the lithium ion conductive particles in the conductive composite membrane. FIG.11B shows an equation for estimating the lithium conductivity of the conductive composite membrane.

[0105] FIG.12 shows a hydrophobic modification of a surface of a lithium ion conductive particle.

[0106] FIGS.13A-13C show schematics of lithium ion conductive particles functionalized with compatibilizing molecules.

[0107] FIG.14 shows a machine that comprises a computer system.

[0108] FIGS.15A-15B show electrolytic cells comprising a conductive composite membrane.

[0109] FIGS.16A-16B show an illustration of a lithium conductive polymer compressing in response to a growing thickness of a lithium metal deposit.

[0110] FIGS.17 shows the potential as a function of time for a water protectivity test.

[0111] FIGS.18 shows NIR experiment results for measuring water content in organic electrolytes.Atty Dkt No.: 65848-720601

[0112] FIG.19A shows a system for extracting lithium from a brine and depositing it onto a conductive substrate.

[0113] FIG.19B illustrates how lithium transport into an organic layer is facilitated by formation of a lithium coordination complex, and how other ions are prevented from entering the organic layer.

[0114] FIG.20 shows how gas formed at the conductive substrate surface can be dispersed away from the surface.

[0115] FIG.21 illustrates an embodiment for which an organic layer is lighter than the brine, and sits atop of the brine, the organic layer being held in place by impermeable barriers.

[0116] FIG.22 illustrates an embodiment for which an organic phase is trapped in an organogel. The organogel can surround a conductive substrate and is submerged in a brine.

[0117] FIG.23 shows a flow diagram for electrochemical extraction of lithium ions from a lithium resource, transfer through a lithium ion permeable membrane into an organic solution containing lithium salt and lithium coordination compound, removal of water molecules, and electroplating onto a cathode.

[0118] FIG.24 illustrates a possible coordination structure of a crown ether and water with lithium ion.

[0119] FIG.25 illustrates a possible coordination structure of cryptand ligand and lithium ion.

[0120] FIG.26 shows experimental results for removing water from an electrolyte using a sorbent.

[0121] FIG.27A-27B show experimental setups and results for removing water from an electrolyte by electrolysis.

[0122] FIGS.28A-28E illustrate embodiments of systems for extracting lithium from a lithium resource. FIG.28A shows an embodiment where water is removed by water electrolysis wherein two electrodes are disposed in an organic solution. FIG.8B shows an embodiment where water is removed by water electrolysis wherein one electrode is disposed in an organic solution and another electrode is disposed in the brine. FIG.28C shows an embodiment where water is removed by trapping in water-absorbing materials such as a molecular sieve. FIG.28D shows an embodiment where water is removed by trapping in water-absorbing materials such as molecular sieves, and wherein the water absorbing materials are stirred in order to speed up the absorption process. FIG.28E shows an embodiment where water molecules are removed by capture as they flow into a water absorbing layer, such as metal oxide framework (MOF) / polymer composite.

[0123] FIG.29 shows representative molecular structures of some non-volatile electrolyte components.Atty Dkt No.: 65848-720601

[0124] FIG.30 show results of experiments where an electrolyte saturated with was dehydrating by pulling the electrolyte under vacuum.

[0125] FIG.31 show results of experiments where an electrolyte saturated with was dehydrating by pulling the electrolyte under vacuum.

[0126] FIG.32 shows a method of extracting lithium from a lithium resource and dehydrating an electrolyte.

[0127] FIG.33 illustrates how an electrolyte can prevent water from contacting lithium metal.

[0128] FIGS.34A-34C illustrate various embodiments of electrolyte configurations for extracting lithium from a lithium resource.

[0129] FIG.35A illustrates a system for extracting lithium from a lithium resource.

[0130] FIG.35B shows further possible processing steps after the lithium metal has been electrodeposited.

[0131] FIG.36 shows some dehydratable electrolytes.

[0132] FIG.37 provides a schematic of a system for electrochemically extracting lithium from a lithium resource.

[0133] FIG.38 show the result of experiments in which lithium was deposited on the working electrode through a non-volatile liquid electrolyte.

[0134] FIG.39 shows a fabrication method of “etching-free” ceramic island.

[0135] FIG.40 shows a fabrication method of “etching-free” ceramic island, or ceramic island which make the etching controllable.

[0136] FIG.41 shows a fabrication method of “etching-free” ceramic island, or ceramic island which make the etching controllable.

[0137] FIG.42 shows a fabrication method of “etching-free” ceramic island, or ceramic island which make the etching controllable.

[0138] FIG.43 shows an electrodialyzer for processing a lithium resource.

[0139] FIG.44 shows an electrodialyzer for processing a lithium resource.

[0140] FIG.45 shows a system for treating a lithium resource comprising LiCl.

[0141] FIG.46 shows a system for treating a lithium resource comprising LiCl.

[0142] FIG.47 shows a system for treating a lithium resource comprising Li2SO4. DETAILED DESCRIPTION

[0143] Lithium brines comprise a significant portion of the Earth’s lithium resource. Brines can be found in various geological formations, as well as seawater, and can comprise a broad range of different compositions and characteristics. As such, brines can pose challenges in extractingAtty Dkt No.: 65848-720601 lithium with high purity and high energy efficiency. Methods are needed for the purification of lithium from dilute sources, the production of smooth, high-purity lithium metal and lithium metal alloys, and the preparation of lithium and lithium alloy anodes for lithium metal batteries.

[0144] One strategy for extracting lithium from brine is to electrodeposit lithium ions in brine on a substrate. FIG.1 shows a system for extracting lithium from brine, in accordance with some embodiments. The system can be used to extract lithium from brine by applying an electric potential between two electrodes. By applying an electric potential, lithium ions can conduct towards an electrode, where they are reduced to form lithium metal. In electrodeposition systems, such as illustrated in FIG.1, water contamination in phases which are in contact with the electrodepositing lithium metal can degrade the lithium metal. Accordingly, it is advantageous to prevent or substantially reduce the presence of water that contacts the lithium metal.

[0145] The transport of water to a working electrode can involve one or more of various mechanisms. Without being bound to a particular theory, it is contemplated that water transportation can occur independently of lithium ion movement and / or correlated with lithium ion movement. See FIG.2A and FIG.2B. In a simplified picture, the two distinct types of water transportation may be influenced by different factors. The transport of free water may be dependent on the concentration of water, convection, etc. The transport of water that forms solvation shells of lithium ions may be dependent on lithium current. See FIG.3. It is also considered that the transport of water constituting solvation shells for non-lithium ions may also occur simultaneously with the movement of these non-lithium ions toward a working electrode.

[0146] A simple electrochemical experiment may demonstrate challenges. FIG.4A shows an illustration of an electrochemical experiment conducted to deposit lithium from brine. Lithium was electrodeposited from brine using a commercially available polymer electrolyte. After running the electrochemical cell for a few hours, lithium from the organic electrolyte was plated onto the working electrode.

[0147] Thus, improved electrochemical methods are needed for the purification of lithium and other electroactive metals from dilute sources, the production of smooth, high-purity lithium metal and lithium metal alloys, and the preparation of lithium and lithium alloy anodes for lithium metal batteries, while preventing water from contacting the electrodeposited lithium. In some aspects, provided herein are strategies for (1) blocking the transport of water to a working electrode, and (2) removing water that is being transported toward the working electrode. FIG. 4B provides an illustration of the two strategies, in accordance with some embodiments.Atty Dkt No.: 65848-720601

[0148] In some embodiments, the blocking can be performed using one or more solid state electrolytes that are configured to prevent the passage of water while permitting the passage of lithium ions through the one or more solid state electrolytes. In some embodiments, the blocking can be performed using one or more liquid electrolytes that are configured to prevent the passage of water while permitting the passage of lithium ions through the one or more liquid electrolytes. The solid electrolytes and the liquid electrolytes can comprise coordination compounds that are configured to increase the conductivity of lithium ions through the electrolytes.

[0149] In some embodiments, the removing can be performed using one or more materials configured to absorb, evaporate, boil, or decompose (electrolyze) water from an electrolyte. In some embodiments, the removing can be performed by electrolyzing water in an electrolyte. In some embodiments, the removing can be performed by bubbling a gas through an electrolyte. In some embodiments, the removing can be performed by applying heat and / or vacuum to a non- volatile electrolyte. SOLID STATE ELECTROLYTES FOR BLOCKING THE PASSAGE OF WATER

[0150] In some aspects, the present disclosure provides systems and methods for blocking the passage of water with solid state electrolytes. A solid state electrolyte can provide a partition between a working electrode configured to reduce lithium ions to lithium metal thereon, and a lithium resource which can be aqueous. In some embodiments, a solid state electrolyte can be configured to selectively conduct lithium ions, while preventing the passage of water. In some embodiments, a solid state electrolyte can comprise a polymer, a ceramic, a coordination compound, or any combination thereof. In some embodiments, a solid state electrolyte can comprise a composite comprising a polymer and a plurality of lithium ion conductive particles. In some embodiments, a solid state electrolyte can comprise a polymer doped or functionalized with coordination compounds, wherein the coordination compounds are configured to conduct lithium ions. Any number and any combination of solid state electrolytes disclosed herein may be employed to reduce or prevent water contamination at the working electrode. For example, a method or system of the present disclosure may use 1, 2, 3, 4, 5, or more solid state electrolytes. The solid state electrolytes may be integrated into a unitary film, e.g., having multiple solid state electrolytes adhered to one another. The solid state electrolytes may be interposed, e.g., two nearest solid state electrolytes may be interposed by a liquid electrolyte.Atty Dkt No.: 65848-720601 COMPOSITE MEMBRANES

[0151] Conductive inorganic membranes (e.g., certain ceramic membranes) can provide a barrier that selectively permits the passage of lithium ions in electrochemical systems. However, it can be challenging and costly to manufacture solid ion conductive membranes while minimizing grain boundaries that constitute defects, which can detrimentally affect the stability and the water permeability of the solid ion conductive membrane. Solid ion conductive membranes can also be brittle, which can make it difficult to manufacture solid ion conductive materials at scale for use in various form factors in electrochemical systems. Accordingly, solid ion conductive materials can be difficult to use for extracting lithium from brine at an industrial scale.

[0152] Meanwhile, lithium ion conductive polymers can be flexible and moldable for various form factors, and may lack certain manufacturing challenges associated with ceramic compositions. However, lithium ion conductive polymers may be hydrophilic and absorb moisture, which can permit the passage of undesirable species (e.g., water or other metal ions) through the lithium ion conductive polymers. Accordingly, lithium ion conductive polymers can be difficult to use for extracting lithium from brine with high purity and quality.

[0153] In some aspects, the present disclosure provides conductive composite membranes, electrochemical systems comprising conductive composite membranes, methods of using thereof, and methods of making thereof. Conductive composite membranes can be used to block the passage of water molecules from a lithium resource, such as brine, to a working electrode when electrodepositing lithium. Conductive composite membranes disclosed herein can comprise a combination of one or more lithium ion conductive particles and a polymer. In some embodiments, the lithium ion conductive particles can comprise a solid ion conductive material. In some embodiments, the polymer can comprise a hydrophobic polymer.

[0154] FIG.5A shows a conductive composite membrane, in accordance with some embodiments. The conductive composite membrane 601 can comprise a hydrophobic film layer 602. The conductive composite membrane can comprise one or more ion conductive particles 603. The one or more lithium ion conductive particles can be embedded in the hydrophobic film layer such that the lithium ion conductive particles are exposed on both sides of the hydrophobic film layer. The conductive composite membrane can thus provide a barrier that selectively permits the passage of lithium ions in electrochemical systems via the lithium ion conductive particles, as shown in FIG.5B. The hydrophobic film layer can provide flexibility and moldability to a composite.

[0155] In some aspects, provided herein is a system for extracting lithium from brine using a conductive composite membrane. FIG.5C shows a system for extracting lithium from brineAtty Dkt No.: 65848-720601 using a conductive composite membrane, in accordance with some embodiments. The conductive composite membrane can be provided in a chamber with brine. The system can comprise an electrode or a current collector 604. The system can comprise a layer 605 between the conductive composite membrane and the electrode or the current collector. The layer can comprise a porous filter, or a portion of the conductive composite membrane 601, or both. The layer can comprise a non-aqueous electrolyte. For example, the layer can comprise a liquid organic electrolyte, a polymer electrolyte, or an organic lithium salt. The system can comprise a chamber 606 comprising brine 607. The brine can be, for example, brine sourced from a geological deposit or seawater. The brine can be provided in raw form, or after having been enriched for lithium or depleted of certain impurities, e.g., sodium or calcium. The system can comprise a counter electrode 608 that can form an electrochemical circuit 609 with the electrode or current collector. The electrochemical circuit can comprise a power source 610 that can apply an electric potential to polarize the counter electrode with a positive electric potential and the electrode or current collector with a negative electric potential. Upon application of the electric potential, lithium ions in the brine can form a current (Arrows), in response to an electric field created by the polarization, that traverses through the one or more ion conductive particles of the conductive composite membrane. Meanwhile, other ions in the brine, which can be considered as impurities, can be substantially prevented or inhibited from forming a part of the current that traverses through the one or more ion conductive particles to come into contact with the electrode or current collector. When the lithium ions contact or come into proximity with the electrode or current collector, lithium ions can be reduced to lithium metal. The conductive composite membrane can be substantially impermeable to water when the system for lithium extraction is in operation, and also when the system is not in operation. The conductive composite membrane can be used for extracting lithium more than once. The deposition of lithium at the electrode or current collector can be substantially free of side reactions caused by water. The deposition of lithium at the electrode or current collector can be substantially free of side reactions caused by other impurities, as the conductive composite membrane can selectively permit the passage of lithium ions. Other impurities that are present in the brine can comprise oxygen, an alkali metal ion, an alkali earth metal ion, sodium salt, magnesium salt, calcium salt, or any combination thereof. In some embodiments, the conductive composite membrane is substantially impermeable to water while electroplating lithium with a thickness of 10 to 50 μm at least 100 times in the system for lithium extraction. In some embodiments, the conductive composite membrane is substantially impermeable to water while electroplating lithium with a thickness of at least 10, 20, 30, 40, or 50 μm; a thickness of at most 10, 20, 30, 40, or 50 μm; atAtty Dkt No.: 65848-720601 least 100, 200, 300, 400, or 500 times; and / or at most 100, 200, 300, 400, or 500 times. The electroplating can be performed using an applied potential of at least about 3, 4, 5, 6, 7, or 8 V. The electroplating can be performed using an applied potential of at most about 3, 4, 5, 6, 7, or 8 V. The electroplating can be performed using a current density of at least about 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, or 50 mA / cm2. The electroplating can be performed using a current density of at most about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, or 50 mA / cm2. The electroplating can be performed at a temperature between about room temperature and the boiling temperature of the brine, about 100 degrees Celsius. The temperature can be at least about 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, or 100 °C. The temperature can be at most about 25, 30, 40, 50, 60, 70, 80, 90, or 100 °C. However, higher temperature is possible by applying high-pressure. Lower temperatures can be associated with fewer occurrences of side reactions, such as the decomposition of electrolyte, solid electrolyte interphase formation, or both. Higher temperatures can increase the conductivity of lithium, may smoothen the lithium metal surface, or both.

[0156] Also provided herein is a rechargeable energy source system comprising a conductive composite membrane. A conductive composite membrane of the present disclosure can be useful for depositing high purity lithium. FIGS.7A-7B show a rechargeable energy source system comprising a conductive composite membrane, in accordance with some embodiments. An advantage of using the conductive composite membrane in a rechargeable energy source system is that the electrode or current collector can be substantially prevented or inhibited from contacting and reacting with non-lithium components (e.g., any organic electrolytes, water, and oxygen) in the rechargeable energy source system, whether the rechargeable energy source system is in operation or not. Reaction of non-lithium components can lead to the loss of active lithium metal, evolution of gaseous species that compromise the safety of the rechargeable energy source system, deterioration / decomposition of electrodes or electrolytes, or any combination thereof. The rechargeable energy source system can comprise an anode 701 and a cathode 702. The rechargeable energy source system can comprise the conductive composite membrane 703 proximal to the anode. The conductive composite membrane can comprise another lithium ion conductive layer between the membrane and the current collector or lithium metal. The rechargeable energy source system can comprise an electrolyte 704 comprising lithium ions. The electrolyte can comprise an aqueous electrolyte or a non-aqueous electrolyte. When the rechargeable energy source system is fully discharged, the conductive composite membrane can be adjacent to or in contact with the anode. The rechargeable energy source system, when in a discharged state, can be charged by the application of an electric potential. As shown in FIG.6A, the anode can be negatively polarized and the cathode can be positivelyAtty Dkt No.: 65848-720601 polarized, which creates an electric field between the anode and the cathode. Upon application of the electric potential, lithium ions in the electrolyte can form a current (Arrows), in response to the electric field created by the polarization, that traverses through the one or more ion conductive particles of the conductive composite membrane. Meanwhile, other components in the electrolyte, such as organic components or water, can be substantially prevented or inhibited from traversing through the one or more lithium ion conductive particles to come into contact with the anode. When the lithium ions contact or come into proximity with the anode, lithium ions can be reduced to lithium metal 705. The lithium metal, when the rechargeable energy source system is fully charged, can comprise a thickness of about 10 μm. The rechargeable energy source system, when in a charged stated as shown in FIG.6B, can be discharged by providing a load 706 that completes an electrochemical circuit. The electrochemical potential difference between the anode and the cathode provides an electrical current through the load, and an ionic current (Arrows) through the electrolyte. Lithium from the anode can be oxidized to lithium ions, which can traverse through the conductive composite membrane, and enter the electrolyte. In some embodiments, the conductive composite membrane can selectively conduct lithium for at least 100 charge-discharge cycles. The charging can be performed using an applied potential of at least about 3 V. The charging or discharging can be performed using a current density of at least about 0.1 mA / cm2.

[0157] In some aspects, the present disclosure provides methods of making conductive composite membranes. In some embodiments, a conductive composite membrane can be manufactured using solvent casting. FIG.7 shows a schematic of a solvent casting method for manufacturing a conductive composite membrane. Lithium ion conductive particles 801 can be dispersed in a polymer solution 802 and spread onto a surface. Solvent in the polymer solution can be evaporated, which can leave a solid composite film 803 with trapped lithium ion conducting particles. The solid polymer film can be etched to provide a conductive composite membrane 804 comprising a polymer film with lithium ion conducting particles dispersed therein. The lithium ion conductive particles can breach two faces of the polymer film. In some cases, conductive composite membranes prepared by a solvent casting method may comprise defects. For example, while the polymer solution is evaporating, solvent can remain in the polymer and become entrapped. Entrapped solvent can reduce the hydrophobicity of the conductive composite membrane, and may allow water to permeate through the conductive composite membrane. In some cases, solvent cast conductive composite membranes can develop gaps between the polymer film and the lithium ion conductive particles. The gaps, which may initially comprise solvent, may leave behind pores when the solvent is further evaporated. InAtty Dkt No.: 65848-720601 some cases, if a high temperature or a strong vacuum is used during evaporation, bubbles may form from boiling solvent, which can create pores. Pores may allow water molecules to pass through the conductive composite membrane. In some cases, it can be difficult to control the thickness of a membrane fabricated using solvent casting. As it can be difficult to prepare thick- enough membranes for certain sizes of lithium ion conductive particles, solvent casting may involve multiple casting times when the particle sizes are large. This process can be difficult to control the resulting thickness so that the thickness is compatible with certain large sizes for the lithium ion conductive particles, while preventing bubbles and trapped solvent.

[0158] In some embodiments, a cast membrane can be dried at high temperatures and / or with annealing. In some cases, drying a solvent cast polymer solution at high temperature can effectively remove solvent molecules, and reduce the water permeability of the manufactured conductive composite membrane. FIG.8 shows a schematic of a solvent casting method with annealing. The solvent cast polymer 902 can be annealed at a temperature above the glass transition temperature of the polymer prior to etching. Annealing above the glass transition temperature can dry out any trapped solvent, and can also allow the polymer chains to reorganize and fill in gaps created by the trapped solvent. Reorganizing of polymer chains can reduce the porosity of the polymer film, fill in gaps between the polymer film and the lithium ion conductive particles, which can also improve adhesion between the polymer film and the lithium ion conductive particles.

[0159] In some embodiments, a conductive composite membrane can be manufactured using hot pressing. FIG.9 shows a schematic of a hot pressing method. Solid hydrophobic polymer beads / pellets 1001 can be mixed with lithium ion conductive particles 1002. Heat and pressure can be applied to the mixture to cause the hydrophobic polymer beads / pellets to transition from a crystalline, semi-crystalline, or glassy state (which can be characterized by effectively frozen macroscopic dynamics) to a softened or a melt state (which can be characterized as capable of flowing). The polymer can flow to envelop the lithium ion conductive particles, and / or the lithium ion conductive particles can penetrate into the polymer in the softened or the melt state. The mixture can be cooled to leave a solid composite film 1003 with embedded lithium ion conductive particles. Applied pressure can help to reduce or to prevent pores in the solid polymer film. The polymer can be etched to expose one or more sides of the lithium ion conductive particles, forming the conductive composite membrane.

[0160] In some embodiments, monomers can be provided in solid or liquid form with the lithium ion conductive particles. The monomers can be reacted to form a polymer around the lithium ion conductive particles. The reactions can be facilitated by heat, light, a catalyst, or anyAtty Dkt No.: 65848-720601 combination thereof. In some embodiments, the monomers can be reacted to form a polymer by applying heat and pressure. The polymer can be etched to expose one or more sides of the lithium ion conductive particles, forming the conductive composite membrane.

[0161] In some embodiments, the conductive composite membrane can be manufactured by hot pressing lithium ion conductive particles into a polymer film. FIG.10 shows a schematic of a method of hot pressing lithium ion conductive particles into a polymer film. Heat and pressure can be applied to polymer beads / pellets 1101 to form a polymer film 1102. Lithium ion conductive particles 1103 can be placed on top of the polymer film, and heat and pressure can be applied. Upon application of heat and pressure, the polymer film can become softened or a polymer melt and permit lithium ion conductive particles to be inserted into the polymer melt. The polymer melt can be cooled to form a composite membrane, and the composite membrane can be etched to form the conductive composite membrane 604. Hot pressing can be hot-pressing or hot-roll-pressing.

[0162] A polymer film can be prepared by hot-pressing polymer pellets into the polymer film. The lithium ion conductive particles can be placed on top of the film, and then hot-pressed into the film. The polymer film of the composite membrane can be etched on both sides to expose the lithium ion conductive particles, thereby forming the conductive composite membrane.

[0163] In some embodiments, the conductive composite membrane can comprise a thickness of 110-140 μm. In some embodiments, the conductive composite membrane can comprise a thickness of at least 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 300, 400, or 500 μm. In some embodiments, the conductive composite membrane can comprise a thickness of at most 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 300, 400, or 500 μm. The thickness can decrease when pressure is applied. The thickness can decrease when the polymer is etched. Etching can, e.g., reduce the thickness of the polymer portion of the conductive composite membrane by at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, or 50 μm. Etching can reduce the thickness of the polymer portion of the conductive composite membrane by at most 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, or 50 μm. The initial thickness of the composite, before etching can be close to the size of the lithium ion conductive particles, e.g., anywhere from 10-20 μm thicker. In some embodiments, etching can comprise solvent etching, acid etching, plasma etching, laser etching, mechanical etching, temperature etching, or any combination thereof.

[0164] Various applied pressures can be used. The magnitude of the applied pressure can depend on a variety of factors, including, the physical properties of the polymer (e.g., viscoelastic properties), the physical properties of the lithium ion conductive particles (e.g., size, shape, Young’s modulus, and elastic limit / breaking stress), the temperature, the duration of appliedAtty Dkt No.: 65848-720601 pressure, or any combination thereof. In some embodiments, the applied pressure can be at least 1 MPa. In some embodiments, the applied pressure can be at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 MPa. In some embodiments, the applied pressure can be at most 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 MPa.

[0165] Various temperatures can be used. The temperature can depend on a variety of factors, including, the physical properties of the polymer (e.g., melting point, glass transition temperature, and decomposition temperature), the physical properties of the lithium ion conductive particles (e.g., size, shape, thermal expansion coefficient, and decomposition or phase transition temperature), or both. In some embodiments, the temperature can be at least 25, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, or 180 degrees Celsius. In some embodiments, the temperature can be at most 25, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, or 180 degrees Celsius. The temperature can be greater than glass transition temperature or melting temperature of the polymer. The temperature can be less than decomposition temperature of the polymer. For example, amorphous cyclic olefin copolymer may have a glass transition temperature of about 80 degrees Celsius, and accordingly, the temperature can be higher than 80 degrees Celsius. On the other hand, for crystalline or semi- crystalline polymers that may have a melting temperature above the glass transition temperature, the temperature can be higher than the melting temperature. The temperature can be less than the melting temperature of lithium metal. The melting temperature of lithium metal at standard conditions is about 180.5 degrees Celsius. Accordingly, the temperature can be less than about 180.5 degrees Celsius. In some embodiments, a temperature refers to a temperature for hot pressing lithium ion conductive particles into a polymer film. In some embodiments, the temperature may be between a glass transition temperature (Tg) and melting temperature (Tm) range of the polymer material. In some embodiments, the temperature provides good particle dispersion and effective film formation. In some embodiments, a temperature refers to a temperature for Li-M deposition. In some embodiments, the temperature may be at least about 20.30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, or 700℃. In some embodiments, the temperature may be at most about 20.30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, or 700℃.

[0166] In some embodiments, the polymer does not conduct lithium ions. In some embodiments, the polymer comprises a hydrophobic polymer. The hydrophobic polymer can comprise, e.g., a cyclic olefin copolymer, fluorinated ethylene propylene, ethylene-methyl acrylate copolymer, perfluoroalkoxy polymer, polymethylpentene, polypropylene, polyphenylene sulfide, polystyrene, polytetrafluoroethylene, polyvinylchloride, polyethylene, ethylene vinyl acetate,Atty Dkt No.: 65848-720601 poly(chlorotrifluoroethylene), polyester, parylene, polycarbonate, polybutadiene or any combination thereof. In some embodiments, the polymer comprises a cyclic olefin copolymer (COC) with a heat deflection temperature of 75 ºC. In some embodiments, the polymer can comprise an olefin polymer. In some embodiments, the polymer can comprise a non-olefin polymer. In some embodiments, the polymer can comprise a cyclic polymer. In some embodiments, the polymer can comprise an acrylic polymer. In some embodiments, the polymer can comprise a copolymer. In some embodiments, the polymer can comprise an amorphous domain. In some embodiments, the polymer can comprise a crystalline domain. In some embodiments, the polymer can comprise a cyclic olefin copolymer. The cyclic olefin copolymer can comprise an amorphous polymer produced by, e.g., copolymerization of cyclic monomers with ethylene. Some examples of cyclic monomers comprise 8,9,10-trinorborn-2-ene (norbornene) and 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (tetracyclododecene). In some embodiments, the cyclic olefin copolymer comprises TOPAS® Advanced Polymers’ TOPAS, or Mitsui Chemical’s APEL®. In some embodiments, hydrophobic alkyl or fluoroalkyl chains may be grafted onto the surface of the polymer matrix to increase it hydrophobicity. In some embodiments, the hydrophobic alkyl or fluoroalkyl chains grafted to the polymer matrix may enhance water blocking capability of the polymer.

[0167] In some embodiments, the conductive composite membrane can comprise low water permeability and low pore volumes. Water permeability of the conductive composite membrane can be measured by various techniques. One technique is Near-Infrared (NIR) spectroscopy. In some embodiments, a NIR measurement can report a water permeability of the conductive composite membrane of less than about 1.0 g / m2･day under 1 mA / cm2. In some embodiments, a NIR measurement can report a water permeability of the conductive composite membrane of less than about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 g / m2･day under a current density of 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 mA / cm2. In some embodiments, a NIR measurement can report a water permeability of the conductive composite membrane as greater than 1.0 g / m2･day under 1 mA / cm2. In some embodiments, a NIR measurement can report a water permeability of the conductive composite membrane as greater than 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 g / m2･day under a current density of 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 mA / cm2. In some embodiments, the composite membrane has a water permeability of less than about 10-10m2s-1Pa-1, 10-15m2s-1Pa-1, 10-18m2s-1Pa-1, or 10-21m2s-1Pa-1under 1 mA / cm2of the current density as measured at least in part by Near-Infrared (NIR) spectroscopy. In some embodiments, the composite membrane has a water permeability of less than about 10-21m2s-1Pa-1under 1Atty Dkt No.: 65848-720601 mA / cm2of the current density as measured at least in part by Near-Infrared (NIR) spectroscopy. Pore volume of the conductive composite membrane can be measured by various techniques. One technique for measuring pore volume is gas pycnometry. In some embodiments, the conductive composite membrane comprises less than about 30% pores by volume. In some embodiments, the conductive composite membrane comprises greater than about 30% pores by volume. In some embodiments, the conductive composite membrane comprises less than about 50, 40, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1% pores by volume. In some embodiments, the conductive composite membrane comprises greater than about 50, 40, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1% pores by volume.

[0168] The conductive composite membrane can comprise a high density ( ^^) of lithium ion conductive particles. In some cases, the lithium conductivity ( ^^^^ ^^+) of the conductive composite membrane can be estimated as the product of the conductivity ( ^^^^ ^^+) times the nominal surface area of the lithium ion conductive particles divided by the nominal surface area of the conductive composite membrane. FIG.11A shows an example of a hexagonal arrangement of the lithium ion conductive particles in the conductive composite membrane. FIG.11B shows an equation for roughly estimating the lithium conductivity of the conductive composite membrane. The actual conductivity can be significantly higher than what is expressed in the equation, because of the 3-dimensional nature of the exposed surfaces of the lithium ion conductive particles and fewer grain boundaries relative to a solid-state membrane of the same material. In some embodiments, the one or more lithium ion conductive particles comprise a particle density of at least about 30%. In some embodiments, the one or more lithium ion conductive particles comprise a particle density of at least about 5, 10, 15, 20, 35, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95%. In some embodiments, the one or more lithium ion conductive particles comprise a particle density of at most about 30%. In some embodiments, the one or more lithium ion conductive particles comprise a particle density of at most about 5, 10, 15, 20, 35, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100%.

[0169] The conductive composite membrane can comprise various values of Li+conductivity. The conductivity can depend on various fabrication parameters, such as the choice of materials, particle density, and other parameters detailed herein. The conductivity can also depend on temperature, as the conductivity usually varies with temperature (e.g., which may be approximated by the Arrhenius relation). The conductivity of the conductive composite membrane can be increased by fabricating it with using polymers that have high decomposition temperatures, which can accordingly be used at high temperatures to conduct lithium ions. In some embodiments, the conductive composite membrane comprises a Li+conductivity of at leastAtty Dkt No.: 65848-720601 about 10-7, 10-6, 10-5, 10-5, 10-4, 10-3, or 10-2S / cm. In some embodiments, the conductive composite membrane comprises a Li+conductivity of at most about 10-7, 10-6, 10-5, 10-5, 10-4, 10-3, or 10-2S / cm. In some embodiments, the conductive composite membrane comprises a Li+conductivity of at least about 1.0 × 10-5S / cm. In some embodiments, the conductive composite membrane comprises a Li+conductivity of at most about 1.0 × 10-5S / cm. In some embodiments, the conductive composite membrane comprises a Li+conductivity of at least about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, or 9 × 10-5S / cm. In some embodiments, the conductive composite membrane comprises a Li+conductivity of at least about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, or 9 × 10-4S / cm. In some embodiments, the conductive composite membrane comprises a Li+conductivity of at least about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, or 9 × 10-3S / cm. In some embodiments, the conductive composite membrane comprises a Li+conductivity of at least about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, or 9 × 10-2S / cm. In some embodiments, the conductive composite membrane comprises a Li+conductivity of at most about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, or 9 × 10-5S / cm. In some embodiments, the conductive composite membrane comprises a Li+conductivity of at most about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, or 9 × 10-4S / cm. In some embodiments, the conductive composite membrane comprises a Li+conductivity of at most about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, or 9 × 10-3S / cm. In some embodiments, the conductive composite membrane comprises a Li+conductivity of at most about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, or 9 × 10-2S / cm. In some embodiments, the conductive composite membrane comprises a Li+conductivity from 10-4to 10-2S / cm. In some embodiments, the conductive composite membrane comprises an activation energy for lithium conductivity of about 0.2 to 0.8 eV. In some embodiments, the conductive composite membrane comprises an activation energy for lithium conductivity that is at least 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, or 0.8 eV. In some embodiments, the conductive composite membrane comprises an activation energy for lithium conductivity that is at most 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, or 0.8 eV. The activation energy can be obtained, e.g., by measuring the lithium conductivity at various temperatures and fitting the measured conductivities to the Arrhenius equation. The slope of the logarithm of conductivity as a function of the inverse temperature can lead to the activation energy.

[0170] The conductive composite membrane can comprise mechanical properties that permit scalability and application in industrial settings. In some embodiments, the conductive composite membrane can comprise a curved form factor. For example, the conductive composite membraneAtty Dkt No.: 65848-720601 can be formed into various shapes, including bended shapes. The conductive composite membrane can be rolled, folded, or etc. In some embodiments, the conductive composite membrane comprises a Young’s modulus of less than about 10 GPa. In some embodiments, the conductive composite membrane comprises a Young’s modulus of less than about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 GPa. In some embodiments, the conductive composite membrane comprises a Young’s modulus of greater than about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 GPa. In some embodiments, the conductive composite membrane is bendable to a radius of curvature of at least about 1 mm without substantially affecting a water impermeability and / or the Li+conductivity of the conductive composite membrane. In some embodiments, the conductive composite membrane is bendable to a radius of curvature of at least about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mm without substantially affecting a water impermeability and / or the Li+conductivity of the conductive composite membrane. In some embodiments, the conductive composite membrane is bendable to a radius of curvature of at most about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mm without substantially affecting a water impermeability and / or the Li+conductivity of the conductive composite membrane.

[0171] In some embodiments, the one or more lithium ion conductive particles can be functionalized with one or more molecules to improve adhesion and / or dispersion in the conductive composite membrane. The one or more molecules can improve adhesion and / or dispersion at by reducing the occurrence of defects at interfaces between the one or more lithium ion conductive particles and the polymer. The defects can be reduced by strengthening the interaction between the one or more lithium ion conductive particles and the polymer. As shown in FIG.12, adhesion can be strengthened by hydrophobically modifying a surface of a lithium ion conductive particle. The hydrophobic modification can be performed by, e.g., incubating the lithium ion conductive particle in a solution with a hydrophobically derivatized silane. In the example shown in FIG.12, the lithium ion conductive particle comprises LICGC, the hydrophobically derivatized silane comprises alkyl chain, and the incubation is performed overnight in an organic. Various other hydrophobically derivatized silanes and other reaction conditions can also be used to improve the adhesion. Various other lithium ion conductive particles can be functionalized.

[0172] The one or more lithium ion conductive particles can be functionalized prior to processing with the polymer or the monomers that form the polymer. In some embodiments, the surfaces of the one or more lithium ion conductive particles can be modified with a reactiveAtty Dkt No.: 65848-720601 group, e.g., a trimethoxy(octadecyl)silane group. The reactive group can then be chemically reacted, in the presence of inorganic materials, to cover the surfaces with one or more adhesive molecules, e.g., alkyl chains. In some embodiments, alkyl chains can provide good compatibility with the base polymer matrix (which can be provided as a film), which can be a cyclic olefin copolymer, which can increase adhesion between the one or more lithium ion conductive particles and the polymer matrix. Various adhesive molecules can be used for various polymer matrices – the adhesive molecules and the polymer matrix can be selected together to provide adhesion between the one or more lithium ion conductive particles and the polymer matrix. For example, some polymer matrices may provide chemically reactive groups, e.g., NH, CO or CN groups. When the polymer matrix comprises chemically reactive groups, the adhesive molecules can be selected that react with the chemically reactive groups to form chemical bonds with the polymer. In some embodiments, the one or more lithium ion conductive particles comprises an adhesive configured to adhere or bind to a hydrophobic polymer matrix. In some embodiments, the adhesive comprises one or more compatibilizing polymer or oligomer molecules that are miscible in the hydrophobic film layer, and are coupled to the one or more lithium conductive particles. For example, the compatibilizing polymer molecules can be hydrophobic such that the compatibilizing polymer molecules solvate in the hydrophobic film layer. Miscibility can be determined based on, e.g., a Flory-Huggins parameter. If the compatibilizing polymer molecules are sufficiently long, they can also entangle with polymer molecules of the hydrophobic film layer. Thus, compatibilizing polymer molecules can improve adhesion of the lithium ion conductive particles into the conductive composite membrane. In some embodiments, the one or more compatibilizing polymer molecules are configured to repel the one or more lithium conductive particles from one another to reduce particle-particle contact between the one or more lithium conductive particles. For example, when a compatibilizing polymer or oligomer molecule of a lithium conductive particle come into proximity with another lithium conductive particle, a repulsive force can arise if the two lithium conductive particles are sufficiently close to reduce the conformational entropy of the polymer molecule. The effect can be called an “entropic spring,” which is illustrated in FIGS.14A-14B, wherein the reduced conformational entropy resulting from compressing or stretching of polymer molecule from an equilibrium distance r0 is disfavored, such that the polymer acts like a “spring” to favor towards states that comprise larger configurational entropy. Thus, lithium ion conductive particles that are functionalized with compatibilizing polymer molecules can promote a certain minimum distance between the lithium ion conductive particles to improve dispersion of the lithium ion conductive particles in the conductive composite membrane. In some embodiments, the one or more lithiumAtty Dkt No.: 65848-720601 conductive particles each comprises at least a distribution of the one or more compatibilizing polymer molecules around the one or more lithium conductive particles, e.g., as shown in FIG. 13C. The lithium ion conductive particles functionalized with compatibilizing polymer molecules can be dispersed by annealing the lithium ion conductive particles above the glass transition temperature of the polymer phase(s) in the membrane.

[0173] In some embodiments, at least one side of the conductive composite membrane can further comprise a lithium conductive polymer. The lithium conductive polymer can be in contact with or be adhered to the conductive composite membrane. The lithium conductive polymer can provide a substantially inert surface in contact with lithium metal, while also providing a medium for lithium ions to conduct through. The lithium conductive polymer can increase uniformity of current distribution for lithium deposition. In some embodiments, the lithium conductive polymer is substantially unreactive with the lithium metal.

[0174] The lithium conductive polymer can be an elastic or a flexible polymer. The growing thickness of the lithium while charging or electrodepositing can be accommodated by an elastic and flexible membrane, which is illustrated in FIGS.16A-16B. As shown in FIGS.16A-16B, the lithium conductive polymer 2002 can compress in response to a growing thickness of the lithium metal deposit 2003. The lithium conductive polymer can be squeezed out to the side. In some embodiments, the expansion of the lithium metal can be accommodated additional by a mechanism, such as a spring in a battery cell. An elastic or flexible lithium conductive polymer which accommodates expansion of lithium metal can improve good contact between lithium and the conductive composite membrane, can provide mechanical support which can suppress dendrite formation on lithium metal, and can homogenize Li+flux toward the lithium metal to plate Li uniformly. In some embodiments, the lithium conductive polymer is a compressible polymer. In some embodiments, the lithium conductive polymer is configured to accommodate for volume changes, which can be created by electrodepositing lithium adjacent to the lithium conductive polymer.

[0175] In some embodiments, the lithium conductive polymer comprises a copolymer. In some embodiments, the lithium conductive polymer comprises a block copolymer. In some embodiments, the lithium conductive polymer comprises a random copolymer, diblock copolymer, a triblock copolymer, a triblock terpolymer, a multiblock copolymer, grafted copolymer, or any combination thereof. In some embodiments, the lithium conductive polymer comprises a grafted random copolymer.

[0176] In some embodiments, a portion of the copolymer is in contact with lithium metal, wherein the portion is substantially unreactive with the lithium metal. A copolymer can, forAtty Dkt No.: 65848-720601 example, be annealed to undergo microphase separation, providing an exposed hydrophobic surface that is substantially unreactive with lithium metal. Meanwhile, the copolymer can further comprise a percolating hydrophilic domain that provides paths for lithium ions to traverse through from one side of the copolymer to the other. In some embodiments, the copolymer can comprise poly(polydimethylsiloxane methacrylate)-b-poly(oligo(ethylene glycol) methacrylate) (PPDMSM-b-POEM). In some embodiments, the copolymer can comprise poly(lauryl methacrylate)-b-POEM, or both.

[0177] The lithium conductive polymer can comprise a glass transition temperature lower than operating temperatures. The lithium conductive polymer can comprise one domain comprising a glass transition temperature lower than operating temperatures, and another domain comprising a glass transition temperature higher than operating temperatures. The lithium conductive polymer can comprise two or more domains each comprising a glass transition temperature lower than operating temperatures.

[0178] The copolymer can comprise a combination of a low-Tghydrophobic polymer (lower than operating temperatures), high-Tg hydrophobic polymer, and a low-Tg lithium-ion conductive polymer. A low-Tg hydrophobic polymer can comprise poly(butyl acrylate) (PBA), poly(butyl methacrylate) (PBMA), poly(lauryl methacrylate) (PLMA), poly(ethylene) (PE), poly(ethylene-alt-propylene) (PEP), poly(urethane) (PU), poly(butadiene) (PB), poly(polyvinylidene methacrylate) (PPVDFMA), poly(perfluoropolyether) (PFPE), poly(perfluoropolyether methacrylate) (PFPEMA), poly(perfluoropolyether acrylate) (PFPEA), or any combination thereof. A high-Tghydrophobic polymer can comprise poly(polytetrafluoroethylene methacrylate) (PPTFEMA), poly(styrene) (PS), poly(methyl methacrylate) (PMMA), polynorbornene (PN), poly(ether ether ketone (PEEK) or any combination thereof. In some embodiments, a low-Tg lithium-ion conductive polymer can comprise poly(poly(ethylene glycol) methacrylate) (PPEGMA), poly(poly(ethylene glycol) acrylate) (PPEGA), poly(perfluoropolyether methacrylate) (PFPEMA), poly(perfluoropolyether acrylate) (PFPEA), poly(fluorinated 1,6-dimethoxyhexane) (PFDMH) or any combination thereof.

[0179] In some embodiments, the copolymer can comprise a combination of a low-Tg (lower than operating temperatures) hydrophobic polymer, and a high-Tglithium-ion conductive polymer. The high-Tg hydrophobic polymer can form glassy, hard, and hydrophobic polymer domains in a copolymer. The mechanical strength imparted by the high-Tg polymer domains can allow designs which decrease the volume fraction of the hydrophobic domains, leading to higher conductivity of the copolymer while maintaining the mechanical stability of the copolymer.Atty Dkt No.: 65848-720601

[0180] In some embodiments, the lithium-ion conductive polymer can comprise a high-Tglithium-ion conductive polymer. For example, the high-Tg lithium-ion conductive polymer can comprise a superionic glass-type Li+conductor.

[0181] In some embodiments, the lithium conductive polymer comprises a glass transition above about room temperature, or above operating temperatures. In some embodiments, the lithium conductive polymer comprises a glass transition temperature lower than about room temperature, or operating temperatures. When the lithium conductive polymer is used below the glass transition temperature, thermal energy can be insufficient to permit large-scale conformational changes in the material (e.g., rearrangement of polymer chains), which can substantially prevent or inhibit large-scale deformations (e.g., melting of the polymer membrane), which can aid in maintaining the mechanical integrity of the polymer membrane. In some cases, the lithium conductive polymer be substantially prevented or inhibited from large-scale deformations when the lithium conductive polymer comprises crosslinks. Crosslinks can be chemical bonds (e.g., C- C bonds, CO-NH bonds, etc.), or physical bonds (e.g., hydrogen bonds, hydrophobic interactions, pi-pi stacking, entanglement, etc.). For example, the lithium conductive polymer can be a copolymer (random, block, graft, etc.) comprising appropriate functional groups that form cross links. PPDMSM-r-POEM, for example, can exhibit rubbery properties with G’ greater than G”, while being conductive to lithium ions. Both PDMSM and POEM can have low Tg, the PPDMSM can create a cross-linked structure via hydrophobic interactions. Furthermore, the polymer topology can be designed such that it provides a large number of physical entanglement of the polymer chains which also can act as a form of physical bonding. The glass transition temperature can be the glass transition temperature of the polymer matrix constituting the lithium conductive polymer. When a copolymer constitutes the lithium conductive polymer and creates microphase separated domains, then the glass transition temperature can be the highest glass transition temperature among two or more domains in the lithium conductive polymer.

[0182] In some embodiments, the lithium conductive polymer comprises mechanically rigid domains. The mechanically rigid domains can comprise a glass transition temperature greater than 20 °C. In some embodiments, the mechanically rigid domains comprise a glass transition temperature greater than 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, or 300 °C. In some embodiments, the mechanically rigid domains comprise a glass transition temperature less than 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, or 300 °C. In some embodiments, the lithium conductive polymer comprises a heat deflection temperature greater than 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, or 300 °C. In some embodiments, the lithium conductive polymerAtty Dkt No.: 65848-720601 comprises a heat deflection temperature less than 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, or 300 °C. The “heat deflection temperature” of a polymer can refer to the temperature at which a sample of the polymer deforms to a specific degree under a specified load. It can be determined by the test procedure outlined in, e.g., ASTM D648.

[0183] The lithium conductive polymer can comprise lithium conducting domains which comprise a glass transition below about room temperature, or below operating temperatures. When the lithium conductive polymer is used above the glass transition temperature of the lithium conducting domains, thermal energy can be sufficient to permit rearrangement of polymer molecules in the lithium conducting domains, which can permit lithium ions more easily traverse through the lithium conducting domains to provide high lithium conductivities. In some embodiments, ion conductive domains of the lithium conductive polymer comprise a glass transition temperature of less than 20 °C. In some embodiments, ion conductive domains of the lithium conductive polymer comprise a glass transition temperature of less than -100, -90, -80, - 70, -60, -50, -40, -30, -20, -10, 0, 10, or 20 °C. In some embodiments, ion conductive domains of the lithium conductive polymer comprise a glass transition temperature of greater than -100, -90, -80, -70, -60, -50, -40, -30, -20, -10, 0, or 10 °C. In some embodiments, ion conductive domains of the lithium conductive polymer comprise a heat deflection temperature greater than -100, -90, -80, -70, -60, -50, -40, -30, -20, -10, 0, 10, or 20 °C. In some embodiments, ion conductive domains of the lithium conductive polymer comprise a heat deflection temperature less than - 100, -90, -80, -70, -60, -50, -40, -30, -20, -10, 0, or 10 °C. For example, PDMS can comprise a glass transition temperature of about -150 °C, PLMA can comprise a glass transition temperature of about -66.3 °C, and PBA can comprise a glass transition temperature of about -43 °C.

[0184] The lithium conductive polymer can provide dimensional stability at and above operating temperatures. The lithium conductive polymer can comprise an apparent melting temperature, which can be defined as the temperature when tan δ = 1 at ω = 1 rad / s of angular frequency as measured through a rheological experiment. The tangent of the phase angle (tan δ = 1) can be obtained by dividing the loss modulus (G') by the storage modulus (G"). When tan δ > 1, the lithium conductive polymer can be considered to be above the apparent melting temperature.

[0185] In some embodiments, the lithium conductive polymer can be a cross-linked elastomer. A cross-linked elastomer can comprise physical crosslinks, chemical crosslinks, or both. The tan δ of a cross-linked elastomer may be less than 1, unless e.g., the elastomer is decomposed by heat.

[0186] In some embodiments, the conductive composite membrane comprises a thermoplastic polymer or a thermoset polymer.Atty Dkt No.: 65848-720601

[0187] In some embodiments, the conductive composite membrane is substantially impermeable to water while electroplating lithium with a thickness of 10 to 50 μm at least 100 times in the system for lithium extraction. In some embodiments, the conductive composite membrane is substantially impermeable to water while electroplating lithium with a thickness of at least 10, 20, 30, 40, or 50 μm; with a thickness at most 10, 20, 30, 40, or 50 μm; at least 100, 200, 300, 400, 500 times; and / or at most 100, 200, 300, 400 or 500 times. The lithium electrodeposition can be performed using an applied potential of at least about 3, 4, 5, 6, 7, 8, 9, or 10 V. The lithium electrodeposition can be performed using an applied potential of at least 3.05 V. The electrodeposition can be performed using an applied potential of at most about 3, 4, 5, 6, 7, 8, 9, or 10 V. The lithium electrodeposition can be performed using a current density of at least about 1 mA / cm2. The lithium electrodeposition can be performed using a current density of at least about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mA / cm2. The lithium electrodeposition can be performed using a current density of at most about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mA / cm2.

[0188] In some embodiments, the conductive composite membrane is impermeable to liquid water and to water vapor for a period of time greater than 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 24 hours when immersed in water. In some embodiments, the conductive composite membrane is impermeable to liquid water and to water vapor for a period of time greater than 1, 2, 3, 4, 5, 6, or 7 days when immersed in water. In some embodiments, the conductive composite membrane is impermeable to liquid water and to water vapor for a period of time greater than 2 or 3 weeks when immersed in water. In some embodiments, the conductive composite membrane is impermeable to liquid water and to water vapor for a period of time less than 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 24 hours when immersed in water. In some embodiments, the conductive composite membrane is impermeable to liquid water and to water vapor for a period of time less than 1, 2, 3, 4, 5, 6, or 7 days when immersed in water. In some embodiments, the conductive composite membrane is impermeable to liquid water and to water vapor for a period of time less than 2 or 3 weeks when immersed in water.

[0189] In some embodiments, the conductive composite membrane is impermeable to liquid water and to water vapor for a period of time greater than 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 24 hours when used to extract lithium from brine under an applied voltage / current of at least about 3.1 V or at least about 1 mA / cm2. In some embodiments, the conductive composite membrane is impermeable to liquid water and to water vapor for a period of time greater than 1, 2, 3, 4, 5, 6, or 7 days when used to extract lithium brine under an applied voltage / current of at least about 3.1 V or at least about 1 mA / cm2. In some embodiments, the conductive composite membrane isAtty Dkt No.: 65848-720601 impermeable to liquid water and to water vapor for a period of time greater than 2 or 3 weeks when used to extract lithium brine under an applied voltage / current of at least about 3.1 V or at least about 1 mA / cm2. In some embodiments, the conductive composite membrane is impermeable to liquid water and to water vapor for a period of time less than 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 24 hours when used to extract lithium from brine under an applied voltage / current of at least about 3.1 V or at least about 1 mA / cm2. In some embodiments, the conductive composite membrane is impermeable to liquid water and to water vapor for a period of time less than 1, 2, 3, 4, 5, 6, or 7 days when used to extract lithium brine under an applied voltage / current of at least about 3.1 V or at least about 1 mA / cm2. In some embodiments, the conductive composite membrane is impermeable to liquid water and to water vapor for a period of time less than 2 or 3 weeks when used to extract lithium brine under an applied voltage / current of at least about 3.1 V or at least about 1 mA / cm2. The applied voltage can be at least 3.1, 3.5, 4, 4.5, 5, 6, 7, 8, 9, or 10 Volts. The applied voltage can be at most 3.5, 4, 4.5, 5, 6, 7, 8, 9, or 10 Volts. The applied current can be at least 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mA / cm2. The applied current can be at most 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mA / cm2.

[0190] In some embodiments, the conductive composite membrane is substantially impermeable to water over at least 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 charge-discharge cycles for a rechargeable energy source system. In some embodiments, the conductive composite membrane is substantially impermeable to water over at most 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 charge-discharge cycles for a rechargeable energy source system. The charge or discharge cycles can be performed using an applied potential of at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 V. The charge or discharge cycles can be performed using an applied potential of at most about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 V. The charge or discharge cycles can be performed using a current density of at least about 1 mA / cm2. The charge or discharge cycles can be performed using a current density of at least about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mA / cm2. The charge or discharge cycles can be performed using a current density of at most about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mA / cm2. ION CONDUCTIVE PARTICLES

[0191] In some embodiments, the one or more lithium ion conducting particles selectively conduct lithium ions. In some embodiments, the one or more lithium ion conducting particles do not conduct non-lithium ions. In some embodiments, the non-lithium ion can be an alkali metal, an alkaline earth metal, a transition metal, a post-transition metal, or a metalloid. In someAtty Dkt No.: 65848-720601 embodiments, the non-lithium ion can be sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, or radium. In some embodiments, a transference number of lithium ions in the one or more lithium ion conducting particles is between 0.9 and 1. In some embodiments, a transference number of lithium ions in the one or more lithium ion conducting particles is at least 0.5, 0.6, 0.7, 0.8, 0.9, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, 0.995, 0.999, 0.9995, or 0.9999. In some embodiments, a transference number of lithium ions in the one or more lithium ion conducting particles is at most 0.5, 0.6, 0.7, 0.8, 0.9, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, 0.995, 0.999, 0.9995, or 0.9999. In some embodiments, a transference number of lithium ions in the one or more lithium ion conducting particles is about 1. In some embodiments, a transference number of the non-lithium ions in the one or more lithium ion conducting particles is between 0 and 0.1. In some embodiments, a transference number of the non-lithium ions in the one or more lithium ion conducting particles is at most 0.5, 0.4, 0.3, 0.2, 0.1, 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, 0.01, 0.005, 0.001, 0.0005, or 0.0001. In some embodiments, a transference number of the non-lithium ions in the one or more lithium ion conducting particles is at least 0.5, 0.4, 0.3, 0.2, 0.1, 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, 0.01, 0.005, 0.001, 0.0005, or 0.0001. In some embodiments, a transference number of the non-lithium ions in the one or more lithium ion conducting particles is about 0.

[0192] In some embodiments, the one or more lithium ion conductive particles comprises a ceramic material. In some embodiments, the ceramic material comprises lithium ion conductive glass ceramic (LICGC), lithium aluminum titanium phosphate (LATP), lithium lanthanum zirconium tantalum oxide (LLZTO), LiFePO4, LiCoO2, lithium-lanthanum titanates (LLTO), garnet type electrolytes, NASICON, LISICON and Thio-LISICON electrolytes, Li7LaZr3O12(LLZO), cubic phase LLZO, or any combination thereof. In some embodiments, the one or more lithium ion conductive particles comprises LATP. Table 2 shows some relevant properties of various lithium ion conductive particles. In some embodiments, higher lithium ion conductivities may be preferred to provide higher conductivity for the conductive composite membrane. In some embodiments, lower thermal expansion coefficient may be preferred to provide better mechanical stability for the conductive composite membrane. Also relevant is the electrochemical stability window, which may be modified by the addition of dopants, to be compatible for the potentials applied during electrodeposition during plating or charging- discharging for rechargeable energy systems. Another consideration is the reactivity of the material to create side reactions with water.

[0193] Table 2. Physical properties of lithium ion conductive particles.Atty Dkt No.: 65848-720601

[0194] The one or more lithium ion conducting particles can comprise various sizes. Smaller particles can reduce the cost of the conductive composite membrane and increase the conductivity. However, when the particles are too small, it may be too difficult to fabricate the conductive composite membrane which provides a structure that the particles can penetrate on both sides, while maintaining mechanical stability and water protectiveness. In some embodiments, the one or more lithium ion conducting particles comprise a size of at least 50 μm. In some embodiments, the one or more lithium ion conducting particles comprise a size of at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, or 500 μm. In some embodiments, the one or more lithium ion conducting particles comprise a size of at most 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, or 500 μm. In some embodiments, the one or more lithium ion conductive particles comprise a dispersity of less than about 0.4, 0.3, 0.2, 0.1, or 0.05. In some embodiments, the one or more lithium ion conductive particles comprise a dispersity of greater than about 0, 0.05, 0.1, 0.2, or 0.3. In some embodiments, the one or more lithium ion conductive particles comprise a dispersity of about 0. 2 The dispersity (Đ) can be defined as Đ = (^^^^) , where σ is the standard deviation and μ is the mean of the size of the particles. In some embodiments, the one or more lithium ion conductive particles comprise a size range of about + / - 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, or 50 μm for at least 50, 60, 70, 80, 90, or 100% of the particles by number. In some embodiments, the one or more lithium ion conductive particles comprise a size range of about + / - 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, or 50 μm for at most 50, 60, 70, 80, 90, or 100% of the particles by number. Dispersity and size range can be measured, e.g., using dynamic light scattering or scanning electron microscopy (SEM).

[0195] In some embodiments, the one or more lithium ion conducting particles comprise a hydrophobically modified surface. The hydrophobic modification can comprise alkyl chains,Atty Dkt No.: 65848-720601 perfluoro chains, fluorinated groups, or any combination thereof. In some embodiments, the one or more lithium ion conducting particles comprise a chemically reactive surface. The chemically reactive surface can comprise OH groups, NH2groups, N3groups, allyl groups, SH groups, or any combination thereof. Chemically reactive groups can be introduced on the surfaces of the one or more lithium ion conductive particles by, e.g., silane coupling. In some embodiments, the one or more lithium ion conducting particles comprise a hydrophilically modified surface. The hydrophilic modification can comprise, e.g., a OH group or a hydrophilic polymer. The hydrophilic polymer can be grafted onto the surfaces of the one or more lithium ion conducting particles. COORDINATION CHEMISTRY FUNCTIONALIZED MEMBRANES

[0196] In some aspects, the present disclosure provides a lithium conductive membrane comprising a polymer. In some embodiments, the polymer is doped or functionalized with a coordination compound. The coordination compound can be configured to coordinate selectively with lithium ions. The polymer (even without the coordination compound) can be a hydrophobic polymer, or otherwise a polymer that is configured to substantially prevent the passage of water through the polymer. Certain hydrophobic polymer may also be non-conductive, or otherwise have conductivity insufficient to be able to effectively transport lithium ions across a membrane made out of the polymer. By adding coordination compounds to the polymer, the polymer may be made to be able to prevent the passage of water while also conducting lithium ions. The coordination compound can comprise any coordination compound disclosed herein.

[0197] In some embodiments, the lithium conductive membrane is configured to provide a water permeability of less than 1.0 g / m2･day as measured at least in part by Near-Infrared (NIR) spectroscopy. In some embodiments, the water permeability is less than 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, or 0.01 g / m2･day. In some embodiments, the water permeability is greater than 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, 0.01, or 0 g / m2･day. In some embodiments, the composite membrane has a water permeability of less than about 10-10m2s-1Pa-1, 10-15m2s-1Pa-1, 10-18m2s-1Pa-1, or 10-21m2s-1Pa-1under 1 mA / cm2of the current density as measured at least in part by Near-Infrared (NIR) spectroscopy. In some embodiments, the composite membrane has a water permeability of less than about 10-21m2s-1Pa-1under 1 mA / cm2of the current density as measured at least in part by Near-Infrared (NIR) spectroscopy. To investigate potential water permeability between an aqueous and an organic electrolyte, a two-chamber system can be assembled utilizing a membrane as a separator. To establish the system, oneAtty Dkt No.: 65848-720601 chamber is filled with a brine solution, such as a LiCl aqueous solution, and the other chamber is filled with an organic electrolyte. A copper working electrode is placed in the organic chamber and a platinum counter electrode is placed in the aqueous chamber, resulting in a configuration of (-) Cu | organic electrolyte | membrane | brine | Pt (+). Subsequently, a constant voltage of -3.0 V or a constant current density of -1.0 mA / cm² is applied to the working electrode. Throughout the experiment, the time-dependent development of water concentration in the organic electrolyte chamber is monitored.

[0198] In some embodiments, the lithium conductive membrane is configured to provide a Li+conductivity of at least about 1.0 × 10-6S / cm at room temperature through the lithium conductive membrane. In some embodiments, the Li+conductivity is at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 × 10-6S / cm at room temperature through the lithium conductive membrane. In some embodiments, the Li+conductivity is less than 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 × 10-6S / cm at room temperature through the lithium conductive membrane.

[0199] In some embodiments, the polymer can be a copolymer. For example, the polymer can be an alternating, random, graft, or block copolymer. In some embodiments, the polymer can comprise a hydrophobic repeating unit. The hydrophobic repeating unit can comprise an acrylate monomer selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, lauryl acrylate, and any combination thereof. The hydrophobic repeating unit can comprise a methacrylate monomer selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, and any combination thereof. The hydrophobic repeating unit can comprise a siloxane monomer selected from the group consisting of dimethyl siloxane, diethyl methoxy siloxane, and any combination thereof. The hydrophobic repeating unit can comprise a fluoroalkyl monomer selected from the group consisting of a perfluoroalkyl monomer, a partially fluorinated monomer, octafluoropentyl acrylate, octafluoropentyl methacrylate, and any combination thereof. The hydrophobic repeating unit can comprise an anionic monomer selected from the group consisting of -(CF2)m- SO2-N--SO2-(CF2)n-CF3 (m = 0-5, n = 0-5), -(CF2)m-SO2-N-SO2-(CHF2)n-CHF2, -(CF2)m-SO2- N--SO2-(CF2)n-CH2F, -COO-, -SO3-, -cyano(trifluoromethanesulfonyl)imide, -2- trifluoromethyl-4,5-dicyanoimidazolide, and any combination thereof. The anionic monomer can be present in a ratio of about 1:1 with the coordination compound. The anionic monomer can be present in a ratio of at least 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 to 1 with the coordination compound. The anionic monomer can be present in a ratio of at most 0.1,Atty Dkt No.: 65848-720601 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 to 1 with the coordination compound.

[0200] In some embodiments, the polymer comprises an additive configured to increase the Li+conductivity. In some embodiments, the additive is hydrophilic. In some embodiments, the additive is hydrophobic. In some embodiments, the additive comprises polyethylene glycol methacrylate. In some embodiments, the polymer comprises a cross-linker.

[0201] The polymer can be functionalized with the coordination compound in an amount sufficient to provide a percolating network of lithium ion conductive paths in the lithium conductive membrane. The amount sufficient to provide the percolating network may be determined by measuring lithium conductivity as a function of concentration of the coordination compound; the slope of conductivity versus concentration may be greater above the percolation concentration compared to below the percolation concentration.

[0202] In some embodiments, the coordination compound can be functionalized to the polymer. The functionalization may be via a vinyl, aldehyde, allylic, acrylate, amine, azide, alkyne, alkene, thiol functional groups, or any other suitable functional group. In some embodiments, the coordination compound can be doped in the polymer without functionalization. The coordination compound can comprise a crown ether, a cryptand, or any other coordination compound disclosed herein. LIQUID ELECTROLYTES FOR BLOCKING THE PASSAGE OF WATER

[0203] In some aspects, the present disclosure provides systems and methods for blocking the passage of water with liquid electrolytes. A liquid electrolyte can provide a partition between a working electrode configured to reduce lithium ions to lithium metal thereon, and a lithium resource which can be aqueous. In some embodiments, a liquid electrolyte can be configured to selectively conduct lithium ions, while preventing the passage of water.

[0204] Any number and any combination of liquid electrolytes disclosed herein may be employed to reduce or prevent water contamination at the working electrode. For example, a method or system of the present disclosure may use 1, 2, 3, 4, 5 or more liquid electrolyte. In some embodiments, a liquid electrolyte can be a non-aqueous electrolyte. In some embodiments, the non-aqueous electrolyte can comprise a coordination compound which are configured to selectively transport lithium ions through the non-aqueous electrolyte.

[0205] In some embodiments, the liquid electrolyte can be disposed above or below the lithium resource. In some embodiments, an electrode is positioned within the liquid electrolyte. In some embodiments, the liquid electrolyte can be contained by an organogel. In some embodiments, anAtty Dkt No.: 65848-720601 electrode is positioned within the organogel, and the organogel contacts the lithium resource. The positioning of the electrode in the liquid electrolyte can (a) protect the electrode from water, thereby substantially reducing or preventing hydrogen gas evolution at the surface of the electrode. The positioning of the electrode in the organic phase can also (b) reduce or prevent the reduction of other metals in the lithium resource in preference to the reduction of Li+to Li metal. The positioning of the electrode in the organic phase can also (c) obviate the need for some costly pre-treatments for separating non-lithium metal ions from the lithium resource, or certain membrane methods to prevent contact of an electrode with water. Moreover, because an electrochemical system can be configured to permit all ion transport to take place in the liquid phase, such transport can be faster compared to methods that may involve ion-selective membrane transport.

[0206] In some embodiments, the liquid electrolyte comprises a fluorinated electrolyte, e.g., FDMB (2,2,3,3-tetrafluoro-1,4-dimethoxylbutane), which can exhibit very high hydrophobicity. The liquid electrolyte, in contact with the aqueous lithium resource, may comprise at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 ppm, and / or at most about 3000, 2000, 1000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 ppm of water during operation, wherein the concentration can be determined using a technique such as 1H NMR, Karl Fischer Titration, or NIR spectroscopy.

[0207] In contrast, certain solvents may not be suitable as the electrolyte, e.g., dichloromethane, because they may not be electrochemically stable during the deposition of lithium. Under certain conditions, dichloromethane may decompose before lithium ion is reduced to form lithium metal. The decomposition products of dichloromethane may further cause side reactions that make deposition uncontrollable or impossible. Dichloromethane may also ignite, as it is a flammable and volatile liquid under ambient conditions, and it is toxic. At 20 degrees Celsius, water may solvate in dichloromethane to up to about 0.24 wt%. Accordingly, the electrochemical stability window of the solvent and biohazard aspects of a solvent may be considered when selecting the liquid electrolyte or a component thereof.

[0208] The selective transport of lithium through the liquid electrolyte can be facilitated by one or more coordination compounds within the organic liquid phase that selectively coordinate lithium cations compared to other metal cations, thereby solubilizing the lithium cation in the liquid electrolyte. The composition of the liquid electrolyte can comprise a water-immiscible electrolyte and a coordination compound. The water-immiscible electrolyte can be an electrochemically stable electrolyte composition in the range of voltages that would need to beAtty Dkt No.: 65848-720601 applied to deposit lithium metal. The water-immiscible electrolyte can be sufficiently hydrophobic so as to reduce water contamination to effectively nil or to acceptably low levels in the electrodeposition system. The water-immiscible electrolyte can be configured to solvate the coordination compound and the complex which it forms with lithium ions.

[0209] The liquid electrolyte can comprise a lithium cation with an organic anion that is soluble in the liquid electrolyte but insoluble in the lithium resource. In some embodiments, the liquid electrolyte can comprise a lithium cation with an inorganic anion (e.g., Cl-) that is soluble in the liquid electrolyte but insoluble in the lithium resource. During electrolysis, lithium ions can be released from the coordination compounds to electroplate onto the surface of the conductive substrate. In order to maintain charge neutrality, lithium ions can be pulled from the lithium resource to bind to the free coordination compounds that have released their lithium ion cargo.

[0210] By using compounds which can selectively coordinate with lithium ions in a lithium resource, the methods and the systems described herein can simplify the process of extracting lithium from the lithium resource (e.g., brine, a type of aqueous lithium resource). Lithium metal can be electrodeposited onto an electrode from the lithium resource, by interposing a liquid electrolyte between the lithium resource and the electrode, wherein the liquid electrolyte is impermeable to water and selectively conducts Li+compared to other ions in the lithium resource. When voltage is applied across a first electrode in the lithium resource and a second electrode across the liquid electrolyte, lithium ions can be transported from the lithium resource, through the liquid electrolyte, to be plated as lithium metal onto the second electrode.

[0211] Certain compounds, such as clathrates and crown ethers, can form molecular “cages” that can envelop and bind to lithium ions. These compounds which can coordinate with lithium ions can be used to concentrate lithium ions in the liquid electrolyte from a lithium resource, while preventing or reducing the amount of water penetration into the liquid electrolyte (e.g., a non- aqueous solvent, e.g., an organic solvent). In some aspects, the present disclosure provides systems, methods, and compositions for using coordination chemistries to concentrate lithium ions by liquid-liquid extraction.

[0212] FIG.19A shows an embodiment of an electrochemical cell. The electrochemical cell 2400 can comprise a cathode comprising a conductive substrate 2402 disposed at the bottom of the electrochemical cell 2400. Covering the conductive substrate 2402 can be a liquid electrolyte (e.g., an organic liquid phase) 2404, comprising an organic solvent that, in this embodiment, is denser than water. The liquid electrolyte 2404 can be immiscible with water. In some embodiments, the liquid electrolyte 2404 can be unreactive with lithium metal. In some embodiments, the liquid electrolyte can form a stable solid electrolyte interface with lithiumAtty Dkt No.: 65848-720601 metal. The liquid electrolyte 2404 can comprise a lithium salt, LiX, which is soluble in the liquid electrolyte by virtue of the lithium cation Li+forming a complex Li(cr)+with a crown ether (cr) or another coordination compound that selectively binds the Li+. The anion X- of the lithium salt can be an organic anion or an inorganic anion that is soluble in the liquid electrolyte but not in water. Likewise, the crown ether or another coordination compound can be soluble in the liquid electrolyte but not in water.

[0213] In some embodiments, the coordination compound (e.g., crown ether) and LiX can be present in the liquid electrolyte in about 1:1 molar ratio, thereby forming a chelate, Li(cr)X, with the coordination compound. In some embodiments, X- is (RSO2)2N-, denoted as RSI- (bis(R- substituted sulfonyl)imide). In some such embodiments, R = -F, -CF3or -(CF2)3CF3.

[0214] In some embodiments, the organic solvent in the liquid electrolyte is CH3OCH2(CF2)nCH2OCH3, where n = 2-6. According to some embodiments, n = 2, and the liquid electrolyte is FDMB (2,2,3,3-tetrafluoro-1,4-dimethoxylbutane). According to some embodiments, n = 4, and the liquid electrolyte is FDMH (2,2,3,3,4,4,5,5-Octafluoro-1,6- dimethoxylhextane). In some embodiments, n is at least 2, 3, 4, 5, or 6, and / or at most 2, 3, 4, 5, or 6.

[0215] In some embodiments, the crown ether has the chemical structure:where R and R’ are pendant organic groups, modulating the solubility of the crown ether. In some embodiments, R and R’ are separately chosen from the group consisting of -(CH2)mCH3and -(CF2)pCF3, where m = 0-10 and p = 0-10. In some embodiments, m is at least 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and / or at most 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, or 0. In some embodiments, p is at least 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and / or at most 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, or 0.

[0216] In some embodiments, the lithium ion selective crown ether is selected from the group consisting of 14-crown-4, substituted derivatives of 14-crown-4, 12-crown-4, substitutedAtty Dkt No.: 65848-720601 derivatives of 12-crown-4, 15-crown-5, substituted derivatives of 15-crown-5, and combinations thereof.

[0217] Disposed above the liquid electrolyte 2404 can be a brine 2406. The brine 2406 can be a lithium resource comprising dissolved lithium cations, Li+(aq). In some embodiments, the brine 2406 is seawater, groundwater, or is derived from seawater or groundwater. Disposed within the brine 2406 can be an anode 2408, connected by an external circuit to the cathode, and configured to allow electrons to flow from the anode to the cathode upon application of voltage across the electrolytic cell.

[0218] In some embodiments, the anode material comprises graphite, platinum, platinized titanium, ruthenium, or iridium.

[0219] Because the anion X- of the lithium salt in the liquid electrolyte 2404 can have a high partition coefficient in the liquid electrolyte vs. the aqueous phase, it can remain confined to the liquid electrolyte 2404 and not migrate to the brine 2406.

[0220] In some embodiments, material making up the conductive substrate 2402 is selected from the group consisting of copper, aluminum, graphite coated copper, graphene coated copper, nickel, stainless steel, platinum, gold, and metal alloys. In some embodiments, the conductive substrate 2402 comprises copper.

[0221] As shown in FIG.19A and FIG.19B, as voltage can be applied across the anode and the conductive substrate to form a layer of lithium metal 2410 deposited on the surface of the conductive substrate 2402. The electrochemical reaction can be described as:

[0222] Li(cr)+(org) + e- = Li (s) + cr (org).

[0223] where “org” denotes that the species is in the liquid electrolyte (e.g., organic phase), “aq” denotes that the species is in the aqueous phase (i.e. the brine), and “s” denotes a solid state species.

[0224] The empty crown ether can then diffuse to the interface between the aqueous and liquid electrolyte to coordinate Li+from the aqueous phase, thereby allowing lithium to enter the liquid electrolyte as a crown ether complex:

[0225] Li+(aq) + cr = Li(cr)+(org).

[0226] In some embodiments, Na+and other larger ions cannot enter the liquid electrolyte because the ring of the crown ether is relatively small, and the larger ions cannot fit in. In some embodiments, anions, such as Cl- and SO42-, cannot enter the liquid electrolyte either, because otherwise the charge neutrality of the liquid electrolyte will be violated. The net cathodic reaction can be described as:

[0227] Li+(aq) + e- = Li (s).Atty Dkt No.: 65848-720601

[0228] The anodic reaction can depend on the composition of the brine. If the anion is predominantly SO42-and / or CO32- / HCO3- the anodic reaction can be described as:

[0229] 2H2O - 4e- = O2↑ + 4H+;

[0230] If the anion is predominantly Cl-, the following electrochemical reaction may also occur:

[0231] 2Cl- - 2e- = Cl2↑.

[0232] An advantage contemplated herein, is that liquid-liquid extraction and electrodeposition can occur together and produce lithium metal from brine in one process, leading to cost and energy savings compared to performing the extraction and the electrodeposition in separate processes. Moreover, the use of a lithium selective liquid electrolyte can provide the following advantages, compared to, e.g., a design using a solid coating on the conductive substrate: (1) As shown in FIG.20, if a small amount of water does transfer from the aqueous phase through the liquid electrolyte, and is reduced at the cathode, the evolved hydrogen may merely bubble up through the liquid electrolyte, causing no significant damage to the cathode. If hydrogen evolves on a cathode with a solid surface coating, the bubbles can damage the coating, leading to potentially catastrophic failure.(2) Because liquid can simply be washed off of the conductive substrate, (e.g., in embodiments illustrated in FIGS.24A-24B), electrochemically formed lithium metal can be more easily recovered than, e.g., solid coating methods.

[0233] As shown in FIG.20, the liquid electrolyte can be denser than the aqueous phase, and may sit on the bottom of the cell. An advantage of this configuration is that any gases that are formed / released at the anode can bubble to the surface of the aqueous phase and escape without reacting with the layer of lithium metal 2410 on the cathode, or causing unwanted mixing of the liquid electrolyte and aqueous lithium resource.

[0234] As shown in FIG.21, a different configuration can be used when the liquid electrolyte is less dense than the aqueous phase. In this embodiment, the liquid electrolyte 2704 can sit atop an aqueous phase 2706 containing lithium salts. The liquid electrolyte 2704 can be held in place on top of the aqueous phase 2706 by impermeable barriers 2712. Situated within the liquid electrolyte can be a conductive substrate 2702 onto which a lithium metal layer 2710 can be deposited. The liquid electrolyte 2704 can be immiscible with water. In some embodiments, the liquid electrolyte 2704 can be unreactive with lithium metal. In other embodiments, the liquid electrolyte 2704 can form a stable solid electrolyte interface with the lithium metal layer 2710. The liquid electrolyte 2704 can comprise a lithium salt, LiX, which is soluble in the liquid electrolyte by virtue of the lithium cation Li+forming a complex Li(cr)+with a crown ether (cr) that selectively binds the Li+. The anion X- of the lithium salt can be an organic anion that isAtty Dkt No.: 65848-720601 soluble in the liquid electrolyte but not in water. Likewise, the crown ether can be soluble in the liquid electrolyte but not in water.

[0235] In the embodiment illustrated in FIG.21, the anode 2708 can be situated away from the liquid electrolyte, in a part of the aqueous phase that is not coated with the liquid electrolyte, so that any bubbles of hydrogen gas 2714 that form may not enter the liquid electrolyte 2704 and may not contact the lithium metal layer 2710. The cathode can be connected by an external circuit 2716 to the conductive substrate 2702, so that when voltage is applied, lithium ion can transport into the liquid electrolyte, forming a complex Li(cr)+with a crown ether (cr), and the Li(cr)+complex can carry the lithium ion to the surface of the cathode, there to be reduced to form the lithium metal layer 2710.

[0236] In the embodiment illustrated in FIG.22, the liquid electrolyte containing the Li(cr)+cation complex can be within an organogel 2804, surrounding the conductive substrate 2802, and submerged within a brine 2806 containing lithium salts. An anode 2808 can be situated away from the organogel 2804, so that any bubbles of hydrogen gas 2814 that form will not enter the organogel 2804 and will not contact the lithium metal layer 2810. The cathode can be connected by an external circuit 2816 to the conductive substrate 2802, so that when voltage is applied, lithium ion can transport into the organogel 2804, forming a complex Li(cr)+with a crown ether (cr), and the Li(cr)+complex can carry the lithium ion to the surface of the cathode, there to be reduced to form the lithium metal layer 2810.

[0237] FIG.23 provides a flow chart of an electrodeposition method for extracting lithium from a lithium resource, in accordance with some embodiments. In some embodiments, an electrochemical cell with a first compartment and a second compartment is prepared with a conductive substrate functioning as a cathode disposed in the first compartment and an anode disposed in the second compartment. In the electrochemical cell, the two compartments can be separated by a lithium ion permeable membrane. A liquid electrolyte can be disposed in the first compartment, such that the cathode is disposed in the liquid electrolyte. The liquid electrolyte can be an organic solution with lithium salts of organic anions and a lithium ion coordinating compound. A means for removing water molecules from the organic solution can also be disposed in the first compartment. A lithium salt containing lithium resource can be disposed in the second compartment, such that the anode is immersed in the lithium resource. Voltage can be applied across the cathode and the anode, plating lithium onto the cathode, at the same time any water that enters the first compartment can be removed by the means for removing the water molecules.Atty Dkt No.: 65848-720601

[0238] As voltage is applied across an anode in the lithium resource and a cathode comprising the conductive substrate, lithium ions can be transported from the lithium resource, through lithium ion permeable membrane, through the liquid electrolyte, and onto the surface of the conductive substrate, where it is reduced and electrodeposited onto the conductive substrate.

[0239] Selective transport of lithium through the organic liquid phase can be facilitating by one or more coordination compounds within the liquid electrolyte. The coordination compounds can selectively coordinate lithium cations compared to other metal cations, thereby solubilizing the lithium cations in the liquid electrolyte. Coordination compounds can comprise clathrates, which trap the lithium cation in a cage structure. Some examples of clathrates comprise crown ethers, and cryptands. In some embodiments, the cryptands are selected from the group consisting of cryptands containing nitrogen, orthoester cryptands, and spherands. The liquid electrolyte can further comprise a lithium cation with an organic anion that is soluble in the liquid electrolyte but insoluble in the brine. During electrolysis, lithium ions can be released from the coordination compounds to electroplate onto the surface of the conductive substrate. In order to maintain charge neutrality, lithium ions can be pulled from the lithium resource to bind to the free coordination compounds that have released their lithium ions. Coordination compounds providing specificity for binding lithium can allow lithium to be pulled into the lithium resource preferentially compared to other cations.

[0240] In some embodiments, the selectivity of lithium ion transport can be sufficiently high to lead to substantially pure lithium to be electroplated onto the surface of the conductive substrate. In some embodiments, the selectivity of lithium transport can be reduced, which can lead to the electroplating of a lithium alloy. By varying the one or more coordination compounds and / or their amounts within the liquid electrolyte, the lithium selectivity can be varied, so that other metal ions from the lithium resource are transported and electroplated onto the conductive substrate in a controlled manner, which can provide control over the composition of the lithium alloy that is electroplated.

[0241] Coordination compounds can be designed to chelate with specific ions. Fine-tuning of pendant groups on the crown ethers can be used to control their solubility in electrolytes. In some embodiments, crown ethers can be optimized to make otherwise organic-solvent-insoluble inorganic salts soluble in organic solvents. Crown ethers can be designed with varied sizes, as well as rigidity and steric hindrance of the molecule that can achieve various degrees of selectivity for lithium ions.

[0242] Certain crown ethers may not provide a full coordination shell for a lithium ion. For example, FIG.24 illustrates how crown ether molecules may provide a roughly planarAtty Dkt No.: 65848-720601 coordination shell for a lithium ion. In this configuration, the top and / or bottom of the complex may be exposed to water or the electrolyte. Thus, water may bind to the coordination complex, and the water may be transported together with the coordination complex to the lithium metal. The presence of water at the lithium metal may cause side reactions, e.g., those that form hydrogen gas evolution, or formation of lithium hydroxide. In some cases, the electrolyte (e.g., 2,2,3,3,4,4,5,5-octafluoro-1,6-dimethoxyhexane; FDMH) may bind to the coordination complex.

[0243] In some embodiments, cryptands may be used as a coordination compound. In some embodiments, cryptand can form a cage configured to selectively coordinate with lithium ions, as shown in FIG.25.

[0244] In some embodiments, the liquid electrolyte can be used to extract at least 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 99.9 percent of lithium in the lithium resource. In some embodiments, the liquid electrolyte can be used to extract at most 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 99.9 percent of lithium in the lithium resource. In some embodiments, the liquid electrolyte extract at least 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 percent of sodium, magnesium, potassium, calcium, or boron from the lithium resource. In some embodiments, the liquid electrolyte extract at most 0, , 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 percent of sodium, magnesium, potassium, calcium, or boron from the lithium resource.

[0245] [[To Michika / Pure Lithium: Would it ever be useful to extract lithium chloride or lithium hydroxide as an intermediate product before electrodepositing lithium metal? If so, how would you do it?]] COORDINATION COMPOUNDS

[0246] Coordination compounds can be configured to form molecular “cages” that can envelop and bind a target chemical entity. Coordination compounds can often provide a high degree of specificity, e.g., discriminating between lithium ions versus magnesium or sodium ions. Suitable coordination compounds comprise clathrates, which can trap the lithium cation in a cage structure. Such clathrates can comprise crown ethers, lariat ethers, multi-armed ethers, calixarenes cryptands, spherands, crytaspherands, hemispherands, and podands. In some embodiments, the cryptands may be nitrogen containing cryptands or orthoester cryptands.

[0247] In some embodiments, the composition can comprise one or more coordination compounds. The one or more coordination compounds can be configured to permit the passage of lithium ions through an electrolyte (liquid or solid) to the electrodepositing lithium metal, without also carrying water molecules through the electrolyte. Without being bound to aAtty Dkt No.: 65848-720601 particular theory, the coordination complex of a lithium ion in the one or more coordination compounds and in the electrolyte may avoid accommodating one or more water molecules. Certain coordination compounds may be capable of coordinating a lithium ion, but they may also solvate water molecules from the aqueous lithium resource. Solvating water molecules can permit the water molecules to contact electrodepositing lithium metal and degrade the lithium metal quality, by turning lithium metal to LiOH or Li+with H2 gas evolution. In some embodiments, the one or more coordination compounds can be configured to completely displace water molecules in the hydration shell of a lithium ion (in the aqueous phase) when accepting the lithium ion into the electrolyte. The one or more coordination compounds can comprise a cryptand, as disclosed herein. The coordination complex of a lithium ion, in the presence of the one or more coordination compounds and / or water, and the dynamics of passage of a lithium ion in hydration shell into the coordination complex in the electrolyte, can be investigated by various experimental and theoretical methods, and rational design. For example, as disclosed herein, the geometry of the coordination complex can be tailored based on the size and shape of the coordination compounds as well as their molecular flexibility. Theoretical or simulation methods such as molecular dynamics simulations or Monte Carlo simulations can provide free energies of solvation for coordination complexes containing zero to a number of water molecules, which can provide the thermodynamic favorability of water incorporation into the coordination complex during operation. Molecular dynamics can be used to investigate the kinetics of lithium ion exchange between the interface between the aqueous phase and the electrolyte, the desolvation of lithium ion in water to its solvation into the coordination complex of the one or more coordination compounds. Various operational parameters can be investigated as well. Experimental methods, such as 1H NMR, Karl Fischer Titration, or NIR spectroscopy, can reveal the level of contamination of water into the electrolyte when the system is operated to deposit lithium.

[0248] In some embodiments, the selectivity of lithium ion transport can permit highly pure lithium being electroplated onto the surface of the conductive substrate. In some embodiments, the selectivity of lithium transport is reduced, leading to the electroplating of a lithium alloy. By varying the nature and amount of the one or more coordination compounds within the electrolyte, the lithium selectivity can be varied, so that other metal ions from the brine are transported and electroplated onto the conductive substrate in a controlled manner, allowing control over the composition of the electroplated lithium alloy.

[0249] In some embodiments, a coordination compound can be a cryptand or a crown ether. Crown ethers can selectively chelate metal ions that fit the size of the “crown”. Moreover, fine-Atty Dkt No.: 65848-720601 tuning of pendant groups on the crown ethers allows control of their solubility in the electrolyte. In particular, crown ethers can be optimized to make otherwise organic-solvent-insoluble inorganic salts soluble in organic solvents. The rigidity and steric hindrance around crown ethers can also be fine-tuned to achieve very high Li+selectivity. Some embodiments of the present disclosure combine liquid-liquid extraction with lithium ion selective crown ethers in tandem with electrolysis to electrodeposit Li metal from brine. Some embodiments of the present disclosure combine solid-liquid extraction with lithium ion selective crown ethers in tandem with electrolysis to electrodeposit Li metal from brine. Likewise, a cryptand or a different coordination compound can be modified or adapted to achieve high Li+selectivity.

[0250] According to some embodiments, the one or more coordination compounds are selected from the group consisting of crown ethers, cryptands, orthoester cryptands, spherands, cryptaspherands, hemisspherands, corands, podands, and combinations thereof. According to some embodiments, the lithium cation coordination compound is a crown ether selected from the group consisting of 15-crown-5, substituted derivatives of 15-crown-5, 14-crown-4, substituted derivatives of 14-crown-4, 12-crown-4, substituted derivatives of 12-crown-4, and combinations thereof.

[0251] Among the alkali metals, lithium cation has both the smallest ionic radius and the most negative hydration free energy (i.e. the strongest affinity for water molecules). Consequently, obtaining selectivity of a coordination compound for lithium ion in aqueous solution compared to other metal cations requires a small cage, strict geometric constraints, and a minimal ability of the cage to rearrange its structure to accommodate larger cations.

[0252] Cryptands can be polycyclic compounds that provide a versatile class of alkali and alkaline earth cation selective cage compounds, and comprise nitrogen containing cryptands and orthoester cryptands. Whereas crown ethers may coordinate guest cations in a single ring, cryptands may “bury” ligands in bicyclic or polycyclic coordination complexes. Spherands can be cryptands that are capable of highly symmetrical coordination of bound ligands. One potential advantage of cryptands compared to crown ethers is that cryptands can occupy all inner sphere coordination sites on a metal cation, whereas crown ethers may not, meaning that for crown ethers some of these coordination sites may be occupied by water or other solvent molecules. Moreover, weaker outer sphere coordination of solvent molecules can potentially occur for any type of coordination complex. As a consequence, if certain coordination complexes are used for liquid-liquid extraction of active metal cations (e.g. lithium) from aqueous solution into an electrolyte, water may be pulled along into the electrolyte. The presence of such water isAtty Dkt No.: 65848-720601 problematic for electrolytic processes in the organic solution involving electroplating of lithium metal as well as other electroactive metals. REMOVING WATER FROM ELECTROLYTES

[0253] In some aspects, the present disclosure provides systems and methods for removing water that is being transported toward the working electrode. In a method for electrochemically extracting lithium from a lithium resource, an electrolyte in an electrochemical system can be dehydrated. The water content in the electrolyte can be maintained below a predetermined threshold. Various methods for removing water from electrolytes are disclosed herein. In some embodiments, the dehydrating can comprise contacting an electrolyte with an adsorbent or an absorbent. In some embodiments, the dehydrating can comprise electrochemically electrolyzing water in an electrolyte. In some embodiments, the dehydrating can comprise bubbling hot gas through an electrolyte. In some embodiments, the dehydrating can comprise heating and / or applying vacuum to an electrolyte to a predetermined temperature and / or pressure.

[0254] In some embodiments, the predetermined threshold is 1000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, or 10 ppm of water as determined using 1H NMR, Karl Fischer titration, or NIR spectroscopy. In some embodiments, the dehydrating in (c) removes at least about 50, 60, 70, 80, 90, 95, 96, 97, 98, 99, 99.1, 99.2, 99.3, 99.4, 99.5, 99.6, 99.7, 99.8, 99.9, 99.91, 99.92, 99.93, 99.94, 99.95, 99.96, 99.97, 99.98, or 99.99% of the amount of water in the electrolyte as determined using 1H NMR, Karl Fischer titration, or NIR spectroscopy. In some embodiments, the dehydrating in (c) removes at most about 60, 70, 80, 90, 95, 96, 97, 98, 99, 99.1, 99.2, 99.3, 99.4, 99.5, 99.6, 99.7, 99.8, 99.9, 99.91, 99.92, 99.93, 99.94, 99.95, 99.96, 99.97, 99.98, 99.99, or 100% of the amount of water in the electrolyte as determined using 1H NMR, Karl Fischer titration, or NIR spectroscopy. ADSORBENTS AND ABSORBENTS

[0255] In some embodiments, the dehydrating can comprise contacting the electrolyte with an adsorbent or an absorbent to remove water from the electrolyte.

[0256] An adsorbent or absorbent can be a material configured to adsorb water from the electrolyte. The adsorbent or absorbent can be a high surface area material, e.g., activated carbon, zeolite, or clay. The adsorbent or absorbent can comprise, e.g., a molecular sieve, aluminum oxide, zeolite, a metal-organic framework (MOF), copper benzene-1,3,5- tricarboxylate (CuBTC), or any combination thereof. In some embodiments, the adsorbent or absorbent comprises zeolite or acid-treated high-purity alumina. FIG.26 shows results ofAtty Dkt No.: 65848-720601 experiments conducted to remove water from an electrolyte using zeolite. After certain periods, the water content in the electrolyte was measured using NIR. Compared to the water content measurable from the electrolyte which has not been treated with a sorbent, the water content using a zeolite and alumina were reduced.

[0257] In some embodiments, an adsorbent or absorbent is configured to remove at least 10, 20, 40, 60, 80, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, or 5000 ppm of water per hour. In some embodiments, an adsorbent or absorbent is configured to remove at most 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, or 10000 ppm of water per hour. WATER ELECTROLYSIS

[0258] In some embodiments, the dehydrating in (c) comprises electrolyzing water in the electrolyte.

[0259] FIG.27A-27B show an experimental setup for electrolyzing water to dehydrate organic electrolyte doped with 1000 ppm of water. An HER electrode was immersed in the liquid electrolyte, and an OER electrode was immersed in a brine. Water-impermeable Li+conductive membrane was used as a separator. A constant potential was applied between a HER electrode and OER electrode. The potential was sufficient to electrolyze water, dehydrating the liquid electrolyte. An NIR probe was immersed in the liquid electrolyte to monitor the water concentration. The results show that the amount of water decreased from about +1000 ppm to - 32 ppm. A negative ppm indicates that the dehydrated electrolyte contains 32 ppm less water than the initial electrolyte.

[0260] To increase the electrolysis rate, one strategy can be to increase the surface area of the electrode immersed in the liquid electrolyte. As the concentration of water in the liquid electrolyte is small to begin with, and becomes vanishingly small as the water is removed, high surface area can improve the rate of water removal by increasing the likelihood of water contacting the electrode. In some embodiments, the electrode can comprise a specific surface area of 5,800 m2 / m3. In some embodiments, the electrode comprises a specific surface area ranging from about 1,000 m2 / m3to about 10,000,000 m2 / m3. In some embodiments, a specific surface area of the electrode is at least about 1,000, 5,000, 10,000, 50,000, 100,000, 500,000, 1,000,000, 5,000,000, or 10,000,000 m2 / m3. In some embodiments, a specific surface area of the electrode is at most about 1,000, 5,000, 10,000, 50,000, 100,000, 500,000, 1,000,000, 5,000,000, or 10,000,000 m2 / m3.Atty Dkt No.: 65848-720601

[0261] Another strategy is to use electrode materials which have higher hydrogen evolution reaction (HER) activities In some embodiments, the electrode can comprise nickel, molybdenum, platinum, or an alloy thereof.

[0262] In certain embodiments, an alternative approach involves the periodic application of voltage or current to counteract cell polarization and / or the electrical double layer at the working electrode. For instance, a continuous voltage application for 10-second intervals could be succeeded by a 1-second resting period. Alternatively, the positive and negative electrodes may be periodically interchanged.

[0263] In some embodiments, another strategy is to make a flow-through organic cell by using a peristatic pump. During electrolysis, H2gas evolved at the HER electrode has the potential to insulate the electrode and increase the internal pressure of the organic chamber. In addition, electrolysis by-product, LiOH, may be precipitated at HER electrode, which can potentially decrease HER activity. At low water ppm, the local concentration of water at the HER electrode may be zero, and thus dehydration may be a diffusion rate-limiting reaction. The flow system can solve all these potential problems.

[0264] In situations where the water electrolysis reaction is transport limited, transportation limitations may be reduced by using a lower viscosity electrolyte (e.g., using viscosity modifiers), providing convection (e.g., stirring the electrolyte using an impeller, creating a flow using a pump), or increasing diffusion (e.g., by increasing temperature). BUBBLING GAS

[0265] In some embodiments, the dehydrating can comprise bubbling gas through the electrolyte. The bubbling gas can comprises a temperature higher than the electrolyte. Higher temperature of the gas can permit the gas to better extract water in the electrolyte. The bubbling gas can comprise an inert gas. The inert gas can be, e.g., argon. The inert gas does not comprise nitrogen. The inert gas is non-reactive with lithium. NON-VOLATILE ELECTROLYTES

[0266] In some embodiments, the dehydrating can comprises evaporating water in the electrolyte. For example, the dehydrating can comprise applying heat, vacuum, or both to the electrolyte. The dehydrating can comprise heating the electrolyte to a predetermined temperature. The dehydrating can comprise applying vacuum to the electrolyte to a predetermined pressure. The electrolyte can be substantially non-volatile at the predetermined temperature, the predetermined pressure, or both. The non-volatile electrolyte may evaporate to aAtty Dkt No.: 65848-720601 negligible degree at the predetermined temperature, the predetermined pressure, or both. FIG.29 shows representative molecular structures of some non-volatile electrolyte components. In some embodiments, the nonvolatile electrolyte may comprise ionic liquids, branched molecules, oligomers, and polymers with conductive side chains or repeating units.

[0267] FIG.30 and FIG.31 show results of experiments where an electrolyte saturated with water was dehydrating by pulling the electrolyte under vacuum. The water contaminated electrolyte was prepared by adding lithium salt to water saturated ionic liquid. The prepared electrolyte was then placed under vacuum (<1.0 mTorr) overnight. The water content in the electrolyte after dehydration was measured by NIR and 1H-NMR. Almost no peak of water was detected by NMR spectroscopy, and the amount of water was outside the detection limit of 1H- NMR. Similar experiments were also performed with 1M LiTFSI in [EMIm][TFSI], 1M LiFSI in [Py13][FSI], 1M LiTFSI in [Py13][TFSI], 1M LiFSI in [Py14][FSI], 1M LiTFSI in [Py14][TFSI], and 4.5 M LiFSI and 1 wt% LiFSI in [Py13][FSI], and water removal was confirmed by NIR and1H-NMR

[0268] FIG.32 shows a method of extracting lithium from a lithium resource and dehydrating a solid state electrolyte. The solid state electrolyte can be provided in contact with a working electrode. By applying a voltage between the working electrode and the counter electrode, lithium can be electrodeposited on the working electrode. The solid state electrolyte can be used to deposit lithium to a predetermined thickness while preventing substantial amount of water from contacting the depositing lithium metal. After a certain thickness of lithium metal has been reached, the solid state electrolyte can be removed, and dehydrated. Then, the solid state electrolyte can be used again for extracting lithium.

[0269] FIG.33 illustrates how an electrolyte can prevent water from contacting lithium metal. An electrolyte can be configured to prevent convection in the electrolyte. For example, the electrolyte can be a liquid electrolyte, solid state electrolyte, or a gel. In some embodiments, the electrolyte may comprise coordination compounds. By preventing convection within the electrolyte, the ionic current of lithium ions may traverse through the electrolyte faster than the diffusion of water in the electrolyte. In some embodiments, the electrolyte may block the penetration of water into electrolyte. In some embodiments, the electrolyte may be dehydrated after depositing a certain thickness of lithium metal.

[0270] FIGS.34A-34C illustrate examples of various embodiments of electrolyte configurations for extracting lithium from a lithium resource. Various modifications and equivalents of the electrolyte configurations described herein will be apparent to those of ordinary skill in the art. In some embodiments, a working electrode can be covered with 1, 2, 3, 4, or any number ofAtty Dkt No.: 65848-720601 electrolyte layers. For example, FIG.34A illustrates an embodiment with two layers of electrolytes. The lithium resource can be in contact with a first polymer electrolyte comprising a coordination compound. The first polymer layer can be configured to block water molecules and selectively conduct lithium ions. In some embodiments, the first polymer layer (polymer 1) is a regenerable electrolyte comprising gel, solid, or liquid. A second polymer layer may follow the first polymer layer. The second polymer layer might not comprise a coordination compound. Instead, the second polymer layer may be configured to be non-reactive with lithium metal, and be lithium ion conducting. In some embodiments, the second polymer layer (polymer 2) is a conductive polymer electrolyte. In some embodiments, the second polymer layer can be used integrated into a battery with the electrodeposited lithium metal. As a result, the electrodeposited lithium metal can be substantially pure and substantially free of side reaction products from water or a reactive polymer. FIG.34B illustrates an embodiment with three layers of electrolytes. The third polymer layer (polymer 3) is a Li+selective membrane, which enables use of natural brines contaminated with various metal cations. FIG.34C illustrates an embodiment comprising multiple layers of electrolytes, including a non-volatile liquid electrolyte. The non- volatile liquid electrolyte can be subject to negative pressure and / or heat which can remove water from the non-volatile liquid electrolyte without substantially degrading or evaporating the non-volatile liquid electrolyte. In some embodiments, in FIG.34C, polymer 1 can be placed next to the polymer 2 or polymer 3.

[0271] FIG.35A illustrates a system for extracting lithium from a lithium resource. In some embodiments, the system can comprise an electrolyte that can be dehydrated by pulling vacuum and / or applying heat. The electrolyte can be a non-volatile liquid electrolyte or a gel electrolyte (e.g., a gel swollen with a non-volatile liquid electrolyte). In some embodiments, the system can comprise a solid state electrolyte adjacent to the working electrode and the electrodepositing lithium metal. The solid state electrolyte can be configured to improve the electrodeposition quality of the lithium metal. In some embodiments, the solid state electrolyte may organize the flow of lithium ions to the working electrode and the growing layer of electrodeposited lithium metal such that the density of the lithium metal is increased, and dendrites are reduced. By using the solid state electrolyte, the non-volatile liquid electrolyte (e.g., an ionic liquid, which may form a solid electrolyte interphase on lithium metal) may be prevented from reacting with the lithium metal. In some embodiments, the solid state electrolyte may form a passivation layer on the lithium metal by reacting with the lithium metal. The non-volatile liquid electrolyte can be used multiple times (e.g., by recycling). For example, the non-volatile liquid electrolyte can be used to deposit a layer of lithium metal having a thickness between 5 μm and 100 μm at leastAtty Dkt No.: 65848-720601 100 times. The system can comprise another solid state electrolyte which is in contact with the lithium resource. The solid state electrolyte can be configured to reduce the amount of water and non-lithium metal cations from entering the non-volatile liquid electrolyte.

[0272] FIG.35B shows further possible processing steps after the lithium metal has been electrodeposited. The non-volatile liquid electrolyte can be dehydrated so that it may be used again for electrodepositing lithium. The working electrode, the lithium metal layer, and the solid state electrolyte may together be integrated into a rechargeable energy source system.

[0273] In some embodiments, the electrolyte comprises a vapor pressure of less than 0.1, 0.01, or 0.001 hPa at 20 °C. In some embodiments, the electrolyte comprises a vapor pressure of greater than 0.01, 0.001, or 0.0001 hPa at 20 °C.

[0274] In some embodiments, the electrolyte comprises a liquid electrolyte. In some embodiments, the electrolyte comprises a solid state electrolyte. For example, the electrolyte can comprise a polymer, an oligomer, an ionic polymer, an ionic dopant, an ionic liquid, a deep eutectic solvent, a gel, or any combination thereof.

[0275] In some embodiments, the electrolyte can be a gel. A gel can be configured to substantially prevent convection in the electrolyte. Preventing convection can have the advantage that the diffusion of water in the electrolyte to the electrode can be limited. In some embodiments, the gel can be swollen with a non-volatile electrolyte. In some embodiments, the gel can be self-healing. When hot gas is bubbled through an electrolyte, a gel can repair itself.

[0276] In some embodiments, the electrolyte comprises an elastomer. In some embodiments, the electrolyte comprises a lithium-ion selective polymer. In some embodiments, the electrolyte is a solid at room temperature. In some embodiments, the electrolyte is a liquid at operating temperatures, wherein the operating temperatures are above 30 °C.

[0277] In some embodiments, the electrolyte comprises succinonitrile, malononitrile, glutaronitrile, adiponitrile, ethylene carbonate, propylene carbonate, diethyl carbonate, trimethylene carbonate, or any combination thereof.

[0278] In some embodiments, the electrolyte can comprise an additive. The additive can be configured to bind with lithium ions in the lithium resource preferentially over the lithium ions binding with water. The additive can configured to form molecular cages around lithium ions. In some embodiments, the additive comprises a coordination compound.Atty Dkt No.: 65848-720601 SYSTEMS FOR EXTRACTING LITHIUM FROM BRINE UNDER DRY ELECTRODEPOSITION CONDITIONS

[0279] Provided herein are various embodiments for blocking water, removing water, or both in electrochemical systems for extracting lithium from a lithium resource.

[0280] In some aspects, the present disclosure provides a system. The system can be configured to extract a metal (e.g., lithium) from a lithium resource, the lithium resource solution having dissolved therein a cation of the metal to be extracted. The system can comprise a first chamber, containing an organic solution, the organic solution having dissolved therein a salt of an organic anion with a cation of the metal to be extracted, and a coordination compound configured to coordinate the cation of the metal to be extracted. The system can comprise a second chamber, containing the lithium resource. Additionally, the system can comprise a cathode disposed in the first chamber, an anode disposed in the second chamber, a first membrane interposed between the organic solution in the first chamber, the lithium resource in the second chamber, and a means for removing water molecules from the organic solution, wherein the cation of the metal to be extracted traverses the first membrane from the lithium resource to the organic solution as voltage is applied.

[0281] The organic solution can comprise a salt of lithium with an organic anion. The coordination compound can be a lithium cation coordination compound that selectively coordinates lithium cation compared to other cations. The lithium resource can comprise an aqueous lithium salt solution.

[0282] The first chamber can be divided into a first sub-chamber and a second sub-chamber. The first sub-chamber can contain the cathode and a first portion of the organic solution. The second sub-chamber can contain a second portion of the organic solution. The system can comprise a second membrane interposed between the first sub-chamber and the second sub-chamber the second membrane, and the second membrane can be permeable to the metal cation. The second portion of the organic solution in the second sub-chamber can be in contact with the first membrane. The means for removing water molecules can be disposed in the second sub- chamber. In some embodiments, the second membrane can be a composite of polymers with water sorbent, such as molecular sieve or metal oxide framework (MOF), the MOF being capable of absorbing water molecules. In some embodiments, the MOF can be copper benzene- 1,3,4,-tricarboxylate (Cu3(BTC)2). In some embodiments, the polymers comprise PVDF-HFP. In some embodiments, the second membrane can be a composite of polymers with zeolite. In some embodiments, the polymers comprise PVDF-HFP. In some embodiments, the second membrane can be a composite of polymers with aluminum oxide.Atty Dkt No.: 65848-720601

[0283] The means for removing water molecules from the organic solution can comprise a pair of electrodes, at least one of the electrodes of the pair being disposed in the organic solution and the other electrode of the pair being disposed in either the organic solution or in the lithium resource. For such embodiments, as voltage is applied across the electrodes, water can be electrolyzed to generate hydrogen and oxygen as gases. A solid substrate that absorbs water can provide the means for removing water molecules from the organic solution. In some embodiments, the solid substrate is a molecular sieve.

[0284] The means for removing water molecules from the organic solution can be selected from the group consisting of (a) deposition at a temperature of between 60 °C and 180 °C, (b) purging of the organic solution with dry argon gas, (c) applying a vacuum to the organic phase, and (d) combinations thereof. In some embodiments, (a) can be carried out in a combination of a higher temperature deposition or other dehydration methods using hot gas, vacuum, electrolysis, and the like, to accelerate a water removal speed.

[0285] The organic solvent can be selected from the group consisting of CH3(CH2)pOCH2(CF2)nCH2O(CH2)qCH3 (n = 1-15, p = 0-15, q = 0-15), alkanes, and combinations thereof. According to some embodiments, the organic solvent can be selected from the group consisting of a liquid polymer and an electrochemically stable ionic liquid.

[0286] In some aspects, the present disclosure provides a method for extracting a metal from a lithium resource containing a cation of the metal to be extracted. The method can comprise applying voltage across a cathode disposed in an organic solution comprising a salt of an organic anion with a cation of the metal to be extracted. The coordination compound can be configured to coordinate the cation of the metal to be extracted. The anode can be disposed in the aqueous salt. The lithium resource can comprise water and a water soluble salt of the metal to be extracted.

[0287] The method can comprise passing the cation of the metal to be extracted through a first membrane from the lithium resource to the organic solution. The method can comprise coordinating the cation of the metal to be extracted with the coordination compound. The method can comprise removing from the organic solution water molecules that traverse the first membrane. The method can comprise depositing the cation of the metal to be extracted on the cathode, thereby causing a layer of the metal to be deposited on the cathode.

[0288] The method can comprise removing the layer of the metal to be extracted from contact with the organic solution. The surface of the layer of the metal can be cleaned. The cleaning may comprise contacting with an organic solvent, for example hexane or dimethyl carbonate. In some embodiments, contacting with an organic solvent comprises operations selected from theAtty Dkt No.: 65848-720601 group consisting of soaking, rinsing, and combinations thereof. In some embodiments, the cleaning may comprise brushing with a soft sponge, followed by sonication in the organic solvent.

[0289] In some embodiments, water can be removed by absorbing water molecules in a metal oxide framework, performing electrolysis to generate hydrogen and oxygen gases, absorbing water molecules in a molecular sieve, or any combination thereof. In some embodiments, the molecular sieve comprises zeolite or activated alumina (aluminum oxide)

[0290] In some embodiments, multiple means may be employed to block or remove water molecules from an electrolyte in contact with lithium metal. FIGS.28A-28E provide illustrative embodiments combining multiple means.

[0291] The embodiments illustrated in FIGS.28-32 can have certain features in common. They can comprise an electrochemical cell 3800 with a first compartment 3801 containing a liquid electrolyte 3802 and a second compartment 3803 containing a lithium resource 3804. A first lithium ion permeable membrane 3805 can separate the first compartment 3801 from the second compartment 3803. Disposed within the first compartment 3801 can be a means of removing water molecules. Immersed in the liquid electrolyte 3802 in the first compartment 3801 can be a cathode 3806, comprising a conductive substrate. Immersed in the lithium resource 3804 of the second compartment 3803 can be an anode 3807. The cathode 3806 and the anode 3807 can be connected by an external electrical circuit configured to provide a voltage 3808 across the cathode 3806 and the anode 3807. In some embodiments, the anode material can comprise graphite or platinum. In some embodiments, material making up the conductive substrate is selected from the group consisting of copper, aluminum, graphite coated copper, nickel, stainless steel, platinum, gold, and metal alloys.

[0292] The liquid electrolyte 3802 can comprise an organic solvent, a lithium ion coordination compound (cc), and an organic lithium salt (LiA), the organic lithium salt comprising an organic anion A- and a lithium cation Li+. The organic solvent, the lithium ion coordination compound and the organic lithium salt can be immiscible in the lithium resource 3804. The lithium ion coordination compound can be primarily present as a lithium ion coordination complex, Li(cc)+. The lithium resource 3804 can be a brine comprising dissolved lithium cations, Li+(aq). In some embodiments, the lithium resource 3804 is derived from seawater.

[0293] According to some embodiments, the coordination compound and Li+are present in the liquid electrolyte at about 1:1 molar ratio. The coordination compound and the lithium ion may form a chelate, Li(cc)+. In some embodiments, A- is (RSO2)2N-, denoted as RSI- (bis(R-Atty Dkt No.: 65848-720601 substituted sulfonyl)imide). In some such embodiments, R = -(CF2)3CF3. Various anions may be used.

[0294] In some embodiments, the organic solvent in the liquid electrolyte can be CH3OCH2(CF2)n,CH2OCH3, where n = 2-5. In some embodiments, n = 2, and the organic solvent comprises FDMB (2,2,3,3-tetrafluoro-1,4-dimethoxylbutane). In some embodiments, the organic solvent comprises FDMH (2,2,3,3,4,4,5,5-octafluoro-1,6-dimethoxyhexane). In some embodiments, the organic solvent comprises FCH2CH2OCH2CH2F (F2DEM), CF3CH2OCH2CH2OCH2CF3 (F6DEE), CHF2CH2OCH2CH2OCH2CHF2 (F4DEE), CHF2CH2OCH2CH2OCH2CF3 (F5DEE), CF3CH2OCH2CH2OCH2CH3 (F3DEE) and any combinations thereof. In some embodiments, the organic solvent may be FCH2CH2OCH2CH2F (F2DEM).

[0295] In some embodiments, the organic solvent in the liquid electrolyte is a solvent with a low vapor pressure. The low vapor pressure solvent can be a liquid polymer, for example low molecular weight polyethylene glycol. In some embodiments, the low vapor pressure solvent is an electrochemically stable ionic liquid. In some embodiments, the electrochemically stable ionic liquid is chosen from the group consisting of N-methyl-N-propyl pyrrolidinium bis(fluorosulfonyl)imide), N-methyl-N-propyl pyrrolidinium bis(fluorosulfonyl)imide, I-ethyl-3 - methylimidazolium bis(fluorosulfonyl)imide, N,N-diethyl-N-(2-methoxyethyl)-N- methylammonium bis(trifluoromethanesulfonyl) imide, and combinations thereof. In some embodiments, the low vapor pressure solvent is branched molecules, for example hexa(methoxyethoxyethoxy)cyclotriphosphazene. In some embodiments, the low vapor pressure solvent is substituted cyclotriphosphazene, substituted polyphosphazene, substituted cyclic siloxane, substituted polydimethylsiloxane. In some embodiments, the low vapor pressure solvent is phosphate ester, cyclic phosphate ester, pentaerythritol ether, branched esters or branched ethers. Substituted molecules, ester group or ether group can be -OCHxFy, - OCH2CHxFy, -O(CH2CH2O)nCHxFy, -OCH2OCHxFy, -OCH2OCH2CHxFy, -OCH2OCHxFy,- OCH2OCH2CHxFy, -O(CH2CH2O)nCH2OCH2CHxFy, -OCH2(CF2)nCH2OCHxFy, - OCH2(CF2)nCH2OCH2OCHxFy, -OCH2(CF2)nCH2OCH2OCH2CHxFy, - OCH2(CF2)nCH2OCH2OCH2CH2OCH2CHxFy, -OCH2(CF2)nCH2OCH2OCH2CH2OCHxFy ((x,y) = (0, 3), (1, 2), (2, 1), or (3, 0), n = 0-15), and any combinations thereof. In some embodiments, the substituted molecules, ester group or ether group may be -OCH2CH2OCH2CH2OCH3.

[0296] In some embodiments, the coordination compound can comprise a crown ether. In some embodiments, the coordination compound comprises a cryptand. In some embodiments, the coordination compound is selected from the group consisting of crown ethers, nitrogen-Atty Dkt No.: 65848-720601 containing cryptands, orthoester cryptands, spherands, cryptaspherands, hemisspherands, corands, podands, and combinations thereof. In some embodiments, the coordination compound is a cryptand selected from the group consisting of a cryptand containing nitrogen, an orthoester cryptand, and a spherand.

[0297] In some embodiments, the coordination compound can be a crown ether having the chemical structure:where R and R’ are pendant organic groups, and wherein their selections may modulate the solubility of the crown ether. In some embodiments, R and R’ are separately chosen from the group consisting of -(CH2)mCH3 and -(CF2)pCF3, where m = 5-10 and p = 0-10. In some embodiments, R and R’ are separately chosen from the group consisting of -CHxFy, -CH2CHxFy, - (CH2CH2O)nCHxFy, -CH2OCHxFy, -CH2OCH2CHxFy, -CH2OCHxFy,- CH2OCH2CHxFy, - (CH2CH2O)nCH2OCH2CHxFy, -CH2(CF2)nCH2OCHxFy, -CH2(CF2)nCH2OCH2OCHxFy, - CH2(CF2)nCH2OCH2OCH2CHxFy, -CH2(CF2)nCH2OCH2OCH2CH2OCH2CHxFy, and - CH2(CF2)nCH2OCH2OCH2CH2OCHxFy((x,y) = (0, 3), (1, 2), (2, 1), or (3, 0), n = 0-15).

[0298] In some embodiments, the coordination compound is selected from the group consisting of 14-crown-4, substituted derivatives of 14-crown-4, 12-crown-4, substituted derivatives of 12- crown-4, and combinations thereof.

[0299] In some embodiments, the coordination compound comprises the [X.Y.Z] cryptand (X = 1-10, Y = 1-10, Z = 1-10) as shown in FIG.25. In some embodiments, the coordination compound has the [1.1.1], [1.1.2], [1.1.3], [1.2.3], [1.3.3], [1.2.2], [2.2.2], [2.2.3], [2.3.3], [3.3.3] core structure, but may be chemically modified with pendant groups.

[0300] When the anion A- of the lithium salt in the liquid electrolyte 3802 can be hydrophobic, it may remain confined to the liquid electrolyte 3802 and may not migrate to the lithium resource 140.Atty Dkt No.: 65848-720601

[0301] Voltage 3808 can be applied across the anode 3807 and the cathode 3808, to deposit a layer of lithium metal 3809 on the surface of the conductive substrate. The electrochemical reaction may be expressed as:

[0302] Li(cc)+(org)+ e- = Li(s)+ cc(org).

[0303] where “org” indicates that the species is in the organic phase (e.g., the liquid electrolyte), and “s” indicates that the species is a solid state species.

[0304] The empty coordination compound cc(org)may diffuse to the second lithium ion permeable membrane 3810 separating the aqueous and organic phases to coordinate Li+from the lithium resource, thereby allowing lithium to enter the liquid electrolyte as a crown ether complex. For example:

[0305] Li+(aq)+ cc(org)= Li(cr)+(org)

[0306] where “aq” indicates that the species is in the aqueous phase (e.g., an aqueous solution of metal salts).

[0307] The lithium ion selectivity of the coordination compound can ensure that lithium ions are preferentially coordinated with the coordination compound, compared to other metal cations in the lithium resource. Anions, such as Cl- and SO42-, may not enter the liquid electrolyte, so that the charge neutrality of the liquid electrolyte is preserved. The net cathodic reaction can be expressed as:

[0308] Li+(aq) + e- = Li(s).

[0309] The anodic reaction can depend on the composition of the lithium resource. If the anion is predominantly SO42-and / or CO32+the anodic reaction may be expected to be:

[0310] 2H2O - 4e- = O2↑ + 4H+;

[0311] If the anion is predominantly Cl-, the following electrochemical reaction may also occur:

[0312] 2C1- - 2e- = Cl2↑.

[0313] The first compartment 3801 can be further divided into a first sub-compartment 3811 and a second sub-compartment 3812, wherein the cathode is disposed within the first sub- compartment 3811, wherein the second sub-compartment 3812 is disposed between the first sub- compartment 3811 and the second compartment 3803, and wherein a second lithium ion permeable membrane 3810 separates the first sub-compartment 3811 from the second sub- compartment 3812. The means of removing water molecules can be disposed in whole or in part in the second sub-compartment 3812. In some embodiments, the sub-compartment 3812 may be further divided into additional sub-compartments, the sub-compartments separated by additional lithium ion permeable membranes. For example, in the embodiment shown in FIG.28D, sub-Atty Dkt No.: 65848-720601 compartment 3812 is separated into two sub-compartments (not labeled) by the lithium ion permeable membrane 3813.

[0314] The means of removing water molecules comprises an electrolytic apparatus 3814 can comprise a pair of electrodes across which a voltage is applied that is sufficient to electrolyze water into hydrogen and oxygen but insufficient to reduce lithium ion to lithium metal. In the embodiment of FIG.28A, the pair of electrodes is disposed in the first compartment. If the first compartment 3801 is further divided into sub-compartments 3811, 3812, then the pair of electrodes may be disposed within the second sub-compartment 3812. In the embodiment of FIG.28B, one of the electrodes is disposed in the lithium resource of the second compartment and the other electrode is disposed in the liquid electrolyte of the first compartment 3801. In some embodiments, adjustment of the voltage can further allow the selective removal of metal ion impurities that are less electropositive than Li+.

[0315] In some embodiments, e.g., as shown in FIG.28C, molecular sieves 3815 provide the means of removing water molecules. In some embodiments, the molecular sieves are packed into the second sub-compartment 3812 of the first compartment, confined between the first lithium ion permeable membrane 3805 and the second lithium ion permeable membrane 3810.

[0316] In some embodiments, e.g., as shown in FIG.28D, molecular sieves comprises the means of removing water molecules. Here the molecular sieves 3815 that are confined to the second sub-compartment 3812 of the first compartment 3801 may not be packed tightly but can be stirred in order to increase the rate of water molecule absorption. In some embodiments, the stirring may be facilitated by one or more magnetic stir-bars 3816. In some embodiments, the second sub-compartment 3812 of the first compartment 3801 is further divided in two, being separated by a third lithium ion permeable membrane 3813, creating two sub-sub-compartments, each of which comprises stirred molecular sieves 3815.

[0317] In some embodiments, e.g., as shown in FIG.28E, the second lithium ion permeable membrane is a metal oxide framework (MOF) 3817, which can function both as the lithium ion permeable lattice and as the means to remove water molecules. The MOF 3817 can be configured to trap water molecules in its lattice, but to allow lithium ions to pass between the first sub-compartment 3811 and the second sub-compartment 3812. In some embodiments the MOF 3817 can be copper benzene-1,3,4,-tricarboxylate (Cu3(BTC)2).

[0318] In some embodiments, the means of water removal is selected from the group consisting of deposition at a high temperature (e.g. between 60 °C and 180 °C), application of a vacuum, bubbling with an inert gas comprising dry argon, and combinations thereof. In some embodiments, the inert gas does not comprise nitrogen. The inert gas is non-reactive withAtty Dkt No.: 65848-720601 lithium. For such embodiments, the organic solvent in the organic liquid phase is a solvent with a low vapor pressure. For some such embodiments, the organic liquid phase is chosen as a solvent with a low vapor pressure. For example, the low vapor pressure solvent is a liquid polymer, such as low molecular weight polyethylene glycol, or an electrochemically stable ionic liquid for example chosen from the group consisting of N-methyl-N-propyl pyrrolidinium bis(fluorosulfonyl)imide), N- methyl-N-propyl pyrrolidinium bis(fluorosulfonyl)imide, 1-ethyl- 3-methylimidazolium bis(fluorosulfonyl)imide, N,N-diethyl-N-(2-methoxyethyl)-N- methylammonium bis(trifluoromethanesulfonyl) imide, and combinations thereof.

[0319] In some embodiments, more than one means of removing water molecules may be combined. For example; means involving high temperature, vacuum, dry argon bubbling, electrolysis, molecular sieves, and metal oxide frameworks may be combined in any or all possible permutations.

[0320] In some embodiments, the organic solution 3802 in the first compartment 3801 is connected to a circulation system which circulates the organic solution 3802 through an external means of water removal.

[0321] In some aspects, the present disclosure provides a system for electrochemically extracting lithium from a lithium resource. The system can comprise an electrochemical cell comprising an electrolyte. The electrochemical cell cab be configured to contact with the lithium resource. The system can comprise a power source configured to apply a current across the electrolyte. The system can comprise a dehydrator. The dehydrator can be configured to dehydrate the electrolyte to maintain water content in the electrolyte below a predetermined threshold.

[0322] FIG.37 provides a schematic of a system for electrochemically extracting lithium from a lithium resource. The system can comprise a solid state electrolyte. The solid state electrolyte can be hydrophobic and lithium ion conducting, such that it blocks the passage of water from the lithium resource. The solid state electrolyte can be fluorinated. The system can comprise a high surface area electrode (e.g., a mesh) and a power source configured to apply an electric potential to the electrode sufficient to electrolyte water in a non-aqueous electrolyte in the system. The system can comprise an adsorbent or an absorbent configured to adsorb or absorb water from the non-aqueous electrolyte. The system can comprise a non-volatile liquid electrolyte which can be dehydrated by applying negative pressure and / or heat.

[0323] In some embodiments, the dehydrator comprises a vacuum, a heater, or both. In some embodiments, the system comprises a channel or a chamber in (i) thermal communication with the heater, (ii) pneumatic communication with the vacuum, or (iii) both, wherein the chamber is configured to receive the electrolyte from the electrochemical cell.Atty Dkt No.: 65848-720601

[0324] In some embodiments, the dehydrator comprises a column containing an adsorbent or an absorbent configured to remove water from the electrolyte, wherein the column is configured to receive the electrolyte from the electrochemical cell. In some embodiments, the dehydrator comprises an electrode configured to electrolyze water in the electrolyte.

[0325] In some embodiments, the electrolyte comprises a non-volatile electrolyte. In some embodiments, the electrolyte comprises a gel. In some embodiments, the electrolyte comprises a coordination compound.

[0326] In some embodiments, the dehydrating can be performed separately from the depositing in (b). In some embodiments, the dehydrating in (c) occurs at a different location from the depositing in (b). In some embodiments, the dehydrating in (c) is performed in a chamber that is separated from a chamber performing the depositing in (b). In some embodiments, the electrolyte remains in the electrochemical cell prior to the dehydrating in (c). In some embodiments, the dehydrating in (c) is performed concurrently with the depositing in (b). In some embodiments, the dehydrating in (c) is performed simultaneously with the depositing in (b). In some embodiments, the dehydrating in (c) is performed in parallel with the depositing in (b). In some embodiments, the dehydrating in (c) is performed at a different time from the depositing in (b). In some embodiments, the dehydrating in (c) is performed prior to the depositing in (b). In some embodiments, the electrolyte is contacted with water before the dehydrating. In some embodiments, the dehydrating in (c) is performed after the depositing in (b). In some embodiments, the dehydration can be performed in the flow line. In some embodiments, the dehydrating can be performed using one or more materials configured to absorb, evaporate, boil, or decompose (electrolyze) water in the flow line. In some embodiments, the dehydration can be performed in the deposition cell. In some embodiments, in the deposition cell, dehydration can be achieved using any of the membranes disclosed herein or any of the electrolytes disclosed herein.

[0327] In some embodiments, the dehydrating can be performed by an inlet and outlet to an organic chamber to circulate the organic electrolyte. After the organic electrolyte is discharged from the outlet, the electrolyte enters the dehydration unit (e.g., electrolytic cell, water absorption column, heat / vacuum drying unit, etc.). If the rate of water removal is fast enough, the organic electrolyte in the chamber can be maintained as anhydrous even if there is some rate of water permeation.

[0328] In some embodiments, the electrolyte is removed from the electrochemical cell prior to the dehydrating in (c). In some embodiments, the electrolyte is cycled through the electrochemical cell during the dehydrating in (c).Atty Dkt No.: 65848-720601 ELECTRODES

[0329] Provided herein are various electrodes or current collectors. As shown in 5C, an electrode can be used in the system for lithium extraction of brine as the electrode or current collector for depositing lithium 604 (the anode) or the counter electrode or current collector 608 (the cathode). As shown in FIGS.7A-7B, an electrode can be used in a rechargeable energy system as the electrode or current collector 701 or the counter electrode (anode) or current collector 702 (cathode).

[0330] In some embodiments, an anode can comprise copper, silicon, silver, carbon, aluminum, gold, or any combination thereof. The carbon can comprise various forms, e.g., a carbon material with roughened surface, graphene, or both. The copper can comprise a copper alloy (e.g., Cu-Zn, Cu-Al, Cu-Sn, or any combination thereof). The anode can comprise one of various lithiophilic metals. The anode can comprise a layer of lithium metal deposited thereon. Lithium metal can be deposited on the anode with a thickness of at least about 10 μm. Lithium metal can be deposited on the anode with a thickness of at least about 1, 5, 10, 20, 30, 40, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 μm. Lithium metal can be deposited on the anode with a thickness of at most about 1, 5, 10, 20, 30, 40, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 μm. Lithium metal can be deposited on the anode with a thickness from 10 to 250 µm.

[0331] In some embodiments, a cathode can comprise vanadium pentoxide, magnesium oxide, iron phosphate, cobalt phosphate, nickel oxide, lithium phosphate, cobalt oxide, nickel manganese cobalt oxide, nickel cobalt aluminum oxide, iron magnesium phosphate, titanium oxide, or any combination thereof. In some embodiments, an electrode comprises an air electrode. The air electrode can be a porous substrate (e.g., a carbon substrate) configured to allow air flow into the electrode from the environment and oxygen flow out of the electrode into the environment. In some embodiments, the air electrode comprises embedded catalysts for oxygen reduction and oxidation. ELECTROLYTES

[0332] Provided herein are various electrolytes. As shown in FIG.5C, an electrolyte can be used in the system for lithium extraction of brine. The electrolyte can comprise the layer, or it can form a component of the layer. For example, the layer can comprise a porous filter or a hydrophobic film layer that is wet with an electrolyte. As shown in FIGS.6A-6B, an electrolyte can be used in a rechargeable energy system as the electrolyte 704 on the cathode side. In some embodiments, the electrolyte may be disposed in a layer 605 between the conductive compositeAtty Dkt No.: 65848-720601 membrane and the electrode or the current collector. In some embodiments, the electrolyte can form a layer of the conductive composite membrane.

[0333] In some embodiments, an electrolyte comprises an aqueous electrolyte. In some embodiments, an electrolyte comprises a non-aqueous electrolyte. In some embodiments, an electrolyte comprises a polymer electrolyte. In some embodiments, an electrolyte comprises an organic electrolyte. In some embodiments, an electrolyte comprises a lithium salt. In some embodiments, an electrolyte comprises an ionic liquid. In some embodiments, an electrolyte comprises a deep eutectic solvent.

[0334] In some embodiments, an electrolyte comprises a decomposition potential of at least 2, 3, 4, 5, 6, 7, 8, 9, or 10 V. In some embodiments, an electrolyte comprises a decomposition potential of at most 2, 3, 4, 5, 6, 7, 8, 9, or 10 V. In some embodiments, an electrolyte comprises a dielectric constant of at least 2, 5, 10, 20, 30, 40, 50, 60, 70, or 80. In some embodiments, an electrolyte comprises a dielectric constant of at most 3, 5, 10, 20, 30, 40, 50, 60, 70, 80, or 90. An electrolyte can comprise various viscosities. Polymeric or polymer solution electrolytes can comprise a large viscosities, as the viscosity can scale exponentially with molecular weight of the polymer above a critical molecular weight (e.g., entanglement molecular weight). In some embodiments, an electrolyte comprises a viscosity of at least 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, or 900 mPa•s. In some embodiments, an electrolyte comprises a viscosity of at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, or 900 Pa•s. In some embodiments, an electrolyte comprises a viscosity of at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, or 900 kPa•s. In some embodiments, an electrolyte comprises a viscosity of at most 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, or 900 mPa•s. In some embodiments, an electrolyte comprises a viscosity of at most 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, or 900 Pa•s. In some embodiments, an electrolyte comprises a viscosity of at most 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, or 900 kPa•s.

[0335] Various organic electrolytes can be used. In some embodiments, an organic electrolyte can comprise dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, 1,3-dioxolan-2-one, 4-methyl-1,3-dioxolan-2-one, oxolan-2-one, and any combination thereof.

[0336] Various polymeric electrolytes can be used. A polymer electrolyte can comprise poly(ethylene oxide), poly(vinyl alcohol), poly(methyl methacrylate), poly(caprolactone),Atty Dkt No.: 65848-720601 poly(chitosan), poly(vinyl pyrrolidone), poly(vinyl chloride), poly(vinyl fluoride), polyvinylidene difluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF- HFP), poly(imide), or any combination thereof, which can inherently conduct lithium ions or be doped with one or more lithium salts to made the polymer be lithium conductive.

[0337] Various ionic liquids can be used, e.g., any one of the ionic liquids listed on the Ionic Liquids Database (ILThermo) of the National Institute of Standards and Technology.

[0338] Various lithium salts can be used. A lithium salt can comprise lithium 12- hydroxystearate, lithium acetate, lithium amide, lithium aspartate, lithium azide, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide (LiFSI), lithium borohydride, lithium bromide, lithium carbonate, lithium chlorate, lithium chloride, lithium citrate, lithium cyanide, lithium diphenylphosphide, lithium hexafluorogermanate, lithium hexafluorophosphate, lithium hypochlorite, lithium hypofluorite, lithium metaborate, lithium methoxide, lithium naphthalene, lithium niobate, lithium nitrate, lithium nitrite, lithium oxalate, lithium perchlorate, lithium stearate, lithium succinate, lithium sulfate, lithium sulfide, lithium superoxide, lithium tantalate, lithium tetrachloroaluminate, lithium tetrafluoroborate, lithium tetrakis(pentafluorophenyl)borate, lithium triflate, lithium tungstate, or any combination thereof.

[0339] Various porous filters can be used. A porous filter can be wet by a liquid electrolyte or an elastic polyelectrolyte. The porous filter can be a relatively soft and flexible material at room or operational temperatures. The softness and flexibility of the filter can provide good contact with ion-conductive particles, underlying substrate (e.g., a current collector like copper foil), and / or good compatibility with lithium metal. The porous filter can suppress dendrite formation, suppress solid electrolyte interphase formation, promote high coulombic efficiency, prevent side- reactions, or etc. LITHIUM RESOURCE

[0340] In some aspects, the present disclosure provides systems and methods of extracting lithium from a lithium resource. A lithium resource can be a natural resource, e.g., a geological resource comprising ore, minerals, or brine, or seawater. A lithium resource can be a salar brine, a salt-lake brine, an oil-field brine, a bromine-plan tail brine, a geothermal brine, a fracking brine, a leachate from mining, an effluent from an industrial process (e.g., from a battery recycling plant), or a combination thereof.

[0341] In some embodiments, the lithium resource comprises an aqueous solution of metal salts comprising (i) a lithium salt and (ii) a sodium salt, a magnesium salt, a calcium salt, a potassium salt, or any combination thereof. In some embodiments, the lithium resource comprises anAtty Dkt No.: 65848-720601 aqueous salt solution. In some embodiments, the lithium resource comprises sodium, potassium, magnesium, calcium, boron, chlorine, SO42-, nitrogen, an alkali metal, an alkali earth metal, or any combination thereof. In some embodiments, the magnesium salt comprises MgCl2. In some embodiments, the sodium salt comprises NaCl. In some embodiments, the lithium resource comprises LiCl, Li2SO4, or both.

[0342] In some embodiments, a ratio of magnesium to lithium in the lithium resource is at least 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 on a molar basis. In some embodiments, a ratio of magnesium to lithium in the lithium resource is at most 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 on a molar basis. In some embodiments, a ratio of magnesium to lithium in the lithium resource is at least 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 on a mass basis. In some embodiments, a ratio of magnesium to lithium in the lithium resource is at most 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 on a mass basis.

[0343] In some embodiments, the lithium resource comprises a total dissolved solid concentration of at least 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, or 100000 mg / L. In some embodiments, the lithium resource comprises a total dissolved solid concentration of at most 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, or 100000 mg / L.

[0344] In some embodiments, the lithium resource is pretreated to remove a metal cation. In some embodiments, the metal cation comprises magnesium, calcium, sodium, potassium, iron, or any combination thereof. In some embodiments, the metal cation is removed by adsorption, extraction, absorption, electrodialysis, precipitation, nanofiltration, solvent extraction, or any combination thereof. In some embodiments, the adsorption or the extraction comprises binding the metal cation to a coordination compound. In some embodiments, the absorption is performed by contacting the lithium resource with lithium-manganese oxide, titanium oxide, aluminum hydroxide, iron phosphate, clay minerals, zeolite, zirconium phosphate, tin antimonate, antimony oxide, tantalum oxide, niobium oxide, or any combination thereof.

[0345] In some embodiments, lithium can be extracted from a geological resource, such as clay and / or ore. In some embodiments, the geological resource can comprise a lithium mineral (e.g., LiAlSi2O6). The geological resource can be treated with sulfuric acid to obtain solutionAtty Dkt No.: 65848-720601 comprising Li2SO4. The Li2SO4can be crystallized or further treated with a base to obtain LiOH (e.g., by adding Ca(OH)2) or Li2CO3 (e.g., by adding Na2CO3). In some embodiments, CaSO4 can be added to the geological resource. In some embodiments, the geological resource can be baked at high temperature. In some embodiments, LiSO4can be extracted using water to obtain an aqueous solution. In some embodiments, the aqueous solution can be concentrated to obtain Li2SO4 as a crystal.

[0346] In some embodiments, the lithium resource or the electrolyte comprises an additive, wherein the additive is configured to bind with lithium ions in the lithium resource preferentially over the lithium ions binding with water. In some embodiments, the lithium resource comprises an anion with a chemical structure of (RS(O)2)2N-, where R is a substituent selected from the group of alkyl, perfluorinated alkyl, partially fluorinated alkyl, aryl, perfluorinated aryl, partially fluorinated aryl, and combinations thereof.

[0347] In some embodiments, the lithium resource comprises at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 20000, 30000, 40000, or 50000 mg / L of lithium. In some embodiments, the lithium resource comprises at most 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 20000, 30000, 40000, or 50000 mg / L of lithium. PRETREAMENT OF LITHIUM RESOURCE

[0348] In some embodiments, a lithium resource can be pretreated. The lithium resource can be limed. Liming can adjust the pH, reduce the concentration of non-lithium components, precipitate phosphorus, precipitate non-lithium metals such as magnesium, or a combination thereof. Precipitates can be separated from the lithium resource by, e.g., solid-liquid separation.

[0349] In some embodiments, a lithium resource can be concentrated. For example, the lithium resource can be concentrated using reverse osmosis. The lithium resource can be boiled to remove water. In some embodiments, the lithium resource can be pretreated to remove organic molecules, remove hydrogen sulfide, precipitate iron, flocculated, filtered to remove solids, or any combination thereof.

[0350] In some embodiments, a lithium resource can be used to generate lithium hydroxide, lithium chloride, lithium carbonate, or any combination thereof. The generated lithium hydroxide, lithium chloride, or lithium carbonate can be in an aqueous solution. The generated lithium hydroxide, lithium chloride, or lithium carbonate can be dried to generate a solid. The dried lithium hydroxide, lithium chloride, or lithium carbonate can be mixed in water to generateAtty Dkt No.: 65848-720601 an aqueous solution comprising lithium ions for making a negative electrode comprising lithium metal. ELECTROLYTES FOR SELECTIVE EXTRACTION OF LITHIUM

[0351] In some embodiments, an electrolyte can be a polymer membrane. In some embodiments, the polymer membrane can comprise a hydrophilic polymer. In some embodiments, the polymer membrane can comprise a hydrophobic polymer. In some embodiments, the polymer can be glassy at room temperature. In some embodiments, the polymer can be a melt at room temperature. In some embodiments, the polymer membrane can selectively conduct and / or diffuse lithium ions over magnesium ions, calcium ions, sodium ions, or any combination thereof. In some embodiments, the polymer membrane can comprise a lithium ion to magnesium ion selectivity of at least 10, 50, 100, 500, 1000, 5000, or 10000. In some embodiments, the polymer membrane can comprise a lithium ion to magnesium ion selectivity of at most 10, 50, 100, 500, 1000, 5000, or 10000. In some embodiments, the polymer membrane can comprise a lithium ion to sodium ion selectivity of at least 10, 50, 100, 500, 1000, 5000, or 10000. In some embodiments, the polymer membrane can comprise a lithium ion to sodium ion selectivity of at most 10, 50, 100, 500, 1000, 5000, or 10000. In some embodiments, the polymer membrane can comprise a lithium ion to calcium ion selectivity of at least 10, 50, 100, 500, 1000, 5000, or 10000. In some embodiments, the polymer membrane can comprise a lithium ion to calcium ion selectivity of at most 10, 50, 100, 500, 1000, 5000, or 10000. For example, the polymer can comprise cellulose. In some embodiments, the polymer can comprise cellulose diacetate, cellulose triacetate, cellulose nitrate, cellulose acetate butyrate, or a combination thereof. The cellulose can be at least 5, 10, 20, 30, 40, 50, 60, 70, or 80 percent acetylated. The cellulose can be at most 5, 10, 20, 30, 40, 50, 60, 70, or 80 percent acetylated.

[0352] In some embodiments, the polymer membrane comprises anisotropic properties. In some embodiments, the polymer membrane comprises a lithium conductivity that is different in the direction perpendicular to the plane of the polymer membrane, compared to the direction that is parallel to the plane of the polymer membrane. For example, when the polymer membrane is spin cast or extruded, the properties of the polymer membrane may be different in the planar direction when the molecules of the polymer become partially aligned due to shear forces. In some embodiments, the polymer membrane can become isotropic when the polymer molecules are given sufficient time to relax and reorganize to an isotropic state.

[0353] In some embodiments, the polymer membrane comprises pores. In some embodiments, the polymer membrane can comprise manufacturing defects which can sporadically introduce airAtty Dkt No.: 65848-720601 bubbles which occupy a certain amount of space in the polymer. In some embodiments, the polymer membrane can be nonporous when the air bubbles are sufficiently annealed out of the polymer membrane.

[0354] In some embodiments, the polymer membrane is semi-crystalline. In some embodiments, the polymer membrane comprises a crystallinity of at least 0, 5, 10, 15, or 20 percent. In some embodiments, the polymer membrane comprises a crystallinity of at most 0, 5, 10, 15, or 20 percent.

[0355] In some embodiments, the polymer membrane can comprise a thickness of at least 0.1, 0.5, 1, 5, 10, 50, 100, 200, 300, 400, or 500 microns. In some embodiments, the polymer membrane can comprise a thickness of at most 0.1, 0.5, 1, 5, 10, 50, 100, 200, 300, 400, or 500 microns. In some embodiments, the polymer membrane comprises a glass transition temperature of at least 25, 50, 75, 100, 250, 450, or 500 °C. In some embodiments, the polymer membrane comprises a glass transition temperature of at most 25, 50, 75, 100, 250, 450, or 500 °C.

[0356] In some embodiments, the polymer membrane is a monovalent selective ion exchange membrane. In some embodiments, electrodialysis can be performed to a lithium resource using a polymer membrane to extract lithium from the lithium resource. In some embodiments, the monovalent selective cation exchange membrane comprises a modified surface. In some embodiments, the modified surface comprises charge moieties to provide a larger Coulombic energy barrier against some ions than other ions. In some embodiments, the membrane is an anion exchange membrane. In some embodiments, the charge moiety can be an amine or an ammonium group. In some embodiments, the anion exchange membrane is configured to selectively extract monovalent anions, such as chlorine or bromine ions, over multivalent anions, such as sulfate ions.

[0357] In some embodiments, an alkyl of the ammonium group of the membrane can be varied to provide different degrees of hydrophobicity. In some embodiments, the ammonium group can be a primary ammonium, a secondary ammonium, a tertiary ammonium, or a quaternary ammonium group. The alkyl group can be a methyl, ethyl, propyl, butyl, pentyl, hectyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or a longer alkyl group.

[0358] In some embodiments, the membrane comprises a water content of at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, or 40 percent by weight in operation. In some embodiments, the membrane comprises a water content of at most 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, or 40 percent by weight in operation. In some embodiments, the membrane comprises a resistivity of at least 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, or 6 Ω ∙ cm2. In some embodiments, the membrane comprises a resistivity of at most 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, or 6 Ω ∙ cm2.Atty Dkt No.: 65848-720601 In some embodiments, the membrane comprises a Donnan potential of at least 1, 2, 3, 4, 5, 10, 15, 20, 25, or 30 mV in operation. In some embodiments, the membrane comprises a Donnan potential of at most 1, 2, 3, 4, 5, 10, 15, 20, 25, or 30 mV in operation. In some embodiments, the membrane can be used with a current density of at least 100, 200, 300, 400, 500, 1000, or 2000 A / m2. In some embodiments, the membrane can be used with a current density of at most 100, 200, 300, 400, 500, 1000, or 2000 A / m2.

[0359] In some embodiments, the membrane is configured to block the transport of protons. In some embodiments, the membrane does not comprise a percolating network of water molecules. In some embodiments, the membrane have an aprotic chemistry. In some embodiments, the membrane comprises polar functional groups capable of conducting lithium ions.

[0360] In some embodiments, an electrolyte can be a liquid. In some embodiments, a liquid electrolyte can be configured to selectively conduct lithium ions over other cations.

[0361] Any number and any combination of liquid electrolytes disclosed herein may be employed to selectively extract lithium from brine. For example, a method or system of the present disclosure may use 1, 2, 3, 4, 5 or more liquid electrolytes. In some embodiments, a liquid electrolyte can be a non-aqueous electrolytes. In some embodiments, the non-aqueous electrolyte can comprise a coordination compound which are configured to selectively transport lithium ions through the non-aqueous electrolyte. In some embodiments, the liquid electrolyte comprises a fluorinated electrolyte, e.g., FDMB (2,2,3,3-tetrafluoro-1,4-dimethoxylbutane)

[0362] By using compounds which can selectively coordinate with lithium ions in a lithium resource, the methods and the systems described herein can simplify the process of extracting lithium from the lithium resource (e.g., brine, a type of aqueous lithium resource). The liquid electrolyte can selectively conduct Li+compared to other cations in the lithium resource. When voltage is applied across a first electrode in the lithium resource and a second electrode across the liquid electrolyte, lithium ions can be transported from the lithium resource, into the liquid electrolyte.

[0363] Certain compounds, such as clathrates and crown ethers, can form molecular “cages” that can envelop and bind to lithium ions. These compounds which can coordinate with lithium ions can be used to concentrate lithium ions in the liquid electrolyte from a lithium resource, while preventing or reducing the amount of other cations into the liquid electrolyte (e.g., Mg2+or Na+). In some aspects, the present disclosure provides systems, methods, and compositions for using coordination chemistries to concentrate lithium ions by liquid-liquid extraction.

[0364] In some embodiments, the electrolyte can be washed with an acidic solution. Washing the electrolyte, which has been enriched in Li+, can extract Li+from the electrolyte.Atty Dkt No.: 65848-720601 MATERIALS FOR SELECTIVE EXTRACTION OF LITHIUM

[0365] In some embodiments, lithium can be extracted from a lithium resource using an adsorbent or an absorbent. In some embodiments, the adsorbent or the absorbent can comprise resins, particles or beads, a column, a packed bed, a membrane, or any combination thereof. In some embodiments, the particles or beads can comprise nanoparticles, microparticles, or both. In some embodiments, the particles or beads can comprise particles having a diameter of at least 1, 2, 3, 4, 5, 6, 7, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 μm. In some embodiments, the particles or beads can comprise particles having a diameter of at most 1, 2, 3, 4, 5, 6, 7, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 μm.

[0366] In some embodiments, the particles in a membrane can comprise a particle density of at least about 30%. In some embodiments, the particles in a membrane can comprise a particle density of at least about 5, 10, 15, 20, 35, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95%. In some embodiments, the particles in a membrane can comprise a particle density of at most about 30%. In some embodiments, the particles in a membrane can comprise a particle density of at most about 5, 10, 15, 20, 35, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100%.

[0367] In some embodiments, the adsorbent or absorbent comprises a membrane. The membrane can be a composite membrane. The composite membrane can have a polymer and a plurality of particles. The composite membrane can be provided on a support. In some embodiments, the polymer can be amorphous or semi-crystalline. In some embodiments, the polymer is a thermoplastic or a thermoset. In some embodiments, the polymer is an entangled polymer. In some embodiments, the polymer comprises cross-linkers. In some embodiments, the polymer comprises a molecular weight of at least 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000 kg / mol. In some embodiments, the polymer comprises a molecular weight of at most 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000 kg / mol. In some embodiments, the polymer comprises polyvinyl chloride, polyethylene, polystyrene, polyurethane, polyester, polymethylmethacylate, or any combination thereof.

[0368] In some embodiments, the membrane can comprise a thickness of at least 0.1, 0.5, 1, 5, 10, 50, 100, 200, 300, 400, or 500 microns. In some embodiments, the membrane can comprise a thickness of at most 0.1, 0.5, 1, 5, 10, 50, 100, 200, 300, 400, or 500 microns.Atty Dkt No.: 65848-720601

[0369] In some embodiments, the polymer or the particles can be functionalized with chelating groups. In some embodiments, the chelating groups are bound to a metal hydroxide or a metal oxide, such as, AlOH3, Al2O3, or both. The metal hydroxide or metal oxide can bind and / or adsorb lithium. In some embodiments, the particles can comprise a metal-organic framework (MOF). A MOF can be configured to bind and / or absorb lithium ions. In some embodiments, the polymer or the particles can comprise a lithium ion exchange resin.

[0370] In some embodiments, the membrane can comprise a flat shape, a tube shape, or a spiral shape. In some embodiments, the membrane comprises a hollow fiber membrane. A plurality of hollow fiber membranes can be formed into a bundle, where the lithium resource can be flowed outside of the bundle, and extracted lithium can flow inside of the hollow fibers. Alternatively, a the lithium resource can be flowed inside of the bundle, and extracted lithium can flow outside of the hollow fibers. The flow on the inside and the outside of the bundle can be in opposite direction, i.e., countercurrent, which can improve the transfer of lithium ions. In some embodiments, the membrane comprises a spiral shape. The membrane can form a spiral around an inner tube.

[0371] In some embodiments, the adsorbent or absorbent is provided in a column. The column can comprise an input port. The column can comprise a flow distributor that is configured to spread a flow from the input into a wider area.

[0372] In some embodiments, the adsorbent or absorbent can comprise an ion exchange material. The ion exchange material can be configured to bind to lithium ions when contacted with the lithium resource. The ion exchange material can be configured to release the lithium ions when contacted with a solution. The solution can be, e.g., water. The solution can comprise a concentration of lithium that is lower than the lithium resource. Having a concentration of lithium that is lower than the lithium resource can allow the lithium in the ion exchange material to release into the second solution. The concentration of lithium in the solution can be less than 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 mg / L of lithium. The concentration of lithium in the solution can be greater than 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 mg / L of lithium. SYSTEMS FOR PRETREATING LITHIUM RESOURCE

[0373] In some embodiments, the pretreating can be performed using a system. The system can comprise a pump configured to pressurize an input flow of the lithium resource. The lithium resource can be pressurized into one or more vessels comprising one or more membranes andAtty Dkt No.: 65848-720601 one or more columns disclosed herein. The one or more membrane and / or the one or more columns can be configured to selectively transport lithium over other cations, or a monovalent anion over other anions. In some embodiments, the one or more membrane and / or the one or more columns can be configured to concentrate lithium by removing water, e.g., by reverse osmosis. The lithium resource can be treated to adjust its pH, filter solids, precipitate non-lithium salts, or any combination thereof before inputting to the system. The output flow from the system can have a lithium purity of at least 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99 percent on a metals basis. The output flow from the system can have a lithium purity of at most 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 99.9 percent on a metals basis. In some embodiments, the system recovers at least 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99 percent of lithium in the lithium resource. In some embodiments, the system recovers at most 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99 percent of lithium in the lithium resource.

[0374] In some embodiments, the system is configured to adjust the pH of the lithium resource. In some embodiments, the pH of the lithium resource can be adjusted to at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14. In some embodiments, the pH of the lithium resource can be adjusted to at most 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14.

[0375] In some embodiments, the system comprises a filter. The filter can be used to remove solids, organics, or descaling the lithium resource. In some embodiments, the system can comprise a water softener. In some embodiments, the system can be configured to remove hydrogen sulfide from the lithium resource.

[0376] In some embodiments, the system can comprise an electrodialyzer. The electrodialyzer can be configured to increase a concentration of lithium in a solution and / or to extract lithium from a lithium resource. The electrodialyzer can be configured to increase a concentration of lithium chloride, lithium hydroxide, or lithium carbonate in the lithium resource.

[0377] FIG.43 shows an example embodiment of an electrodialyzer. The electrodialyzer can comprise two flowing streams. One stream can be a lithium resource. The other stream can be another solution, e.g., water. The other stream can also be the lithium resource. The flowing streams can be partitioned by a membrane. The membrane can be a lithium selective membrane. An electrical potential can be applied, using electrodes, across the flowing streams and membrane to transport ions across the membrane. Lithium can be transported across the membrane from one stream to the other. Anions can be transported across the membrane from one stream to the other. One stream can become enriched in lithium, while the other stream can become depleted in lithium. Current can be maintained by electrochemical reactions at theAtty Dkt No.: 65848-720601 electrodes. For example, hydrogen evolution, oxygen evolution, chlorine evolution, may occur at the electrodes to provide electrical current.

[0378] FIG.44 shows another embodiment of an electrodialyzer. In some embodiments, the electrodialyzer can comprise three flowing streams. One stream can be a lithium resource. The other streams can be another solution, e.g., water. The flowing streams can be partitioned by at least two membranes. The first membrane can be a lithium selective membrane, which partitions the lithium resource from one of the flowing streams. The second membrane can be an anion selective membrane (e.g., selective for chlorine ions), which partitions the lithium resource from another one of the flowing streams. An electrical potential can be applied, using electrodes, across the flowing streams and membrane to transport ions across the membrane. Lithium can be transported across the first membrane from the lithium resource to the flowing stream closer to the negative electrode. Meanwhile, chlorine ions can be transported across the second membrane from the lithium resource to the flowing stream closer to the positive electrode.

[0379] FIG.45 shows a system for treating a lithium resource comprising LiCl. In some embodiments, treating the lithium resource can produce LiOH, H2, and / or Cl2. The system can comprise a cation selective membrane. The cation selective membrane can block the transport of anions across the membrane. Li+can be transported towards the negatively charged electrode. LiOH can be produced with the aid of electrolytic reaction of water. The Cl2 gas can be produced at a positively charged electrode. The H2 gas can be produced at a negatively charged electrode.

[0380] FIG.46 shows a system for treating a lithium resource comprising LiCl. In some embodiments, treating the lithium resource can produce LiOH, H2, and / or Cl2. The system can comprise a cation selective membrane. The system can comprise a cation selective membrane a Li+selective membrane. The system can selectively transport Li+across the membrane over other cations such as Na+, Mg2+, and Ca2+. Li+can be transported towards the negatively charged electrode. LiOH can be produced with the aid of electrolytic reaction of water. The Cl2 gas can be produced at a positively charged electrode. The H2 gas can be produced at a negatively charged electrode.

[0381] FIG.47 shows a system for treating a lithium resource comprising Li2SO4. In some embodiments, treating the lithium resource can produce LiOH, H2, O2, and / or H2SO4. The system can comprise a cation selective membrane. The cation selective membrane can block the passage of anions, such as SO42-. The system can comprise an anion selective membrane. The anion selective membrane can block the passage of cations, such as Li+. Li+can be transported towards the negatively charged electrode. LiOH can be produced with the aid of electrolytic reaction of water. The H2gas can be produced at a negatively charged electrode. The O2gas canAtty Dkt No.: 65848-720601 be produced at a positively charged electrode. The H2SO4can be produced at a positively charged electrode.

[0382] LITHIUM METAL

[0383] Lithium metal electrodes for lithium metal batteries can comprise a thin layer (usually < 50 µm thick) of lithium metal on a conductive substrate. Some processes for manufacturing lithium metal electrodes from brine can take multiple steps, including purification of brine, electrolysis of molten LiCl, and extrusion of Li ingots into thin films on copper.

[0384] In some embodiments, a lithium metal electrode has a specific capacity of greater than about 3500, 3600, 3700, 3750, or 3800 mAh per gram. In some embodiments, a lithium metal electrode has a specific capacity of less than about 3600, 3700, 3750, or 3800 mAh per gram. The overall capacity of the lithium metal electrode (e.g., in basis of mAh) can be substantially matched with the capacity of the cathode. In some embodiments, a lithium metal electrode has a density of between about 0.4 g / cm3and about 0.534 g / cm3. In some embodiments, lithium metal electrode has a density of between about 0.45 g / cm3and about 0.543 g / cm3. In some embodiments, lithium metal electrode has a density of greater than 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, or 0.53 g / cm3. In some embodiments, lithium metal electrode has a density of less than 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, or 0.543 g / cm3.

[0385] Lithium metal can comprise less than 1000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of a non-metallic element. The ppm can be by mass or by count. The ppm can correspond to a basis used for the instrument to detect the non-metallic element. Lithium metal can comprise less than 5 parts-per-million (ppm) of non-metallic elements. In some embodiments, the lithium metal comprises no more than 1 ppm of non-metallic elements by mass. The non-metallic element can be nitrogen, boron, oxygen, carbon, hydrogen, or fluorine. Non-metallic elements can be present as atomic species, or molecular species (e.g., as Li3N, OH, lithium-boron compounds, carbonate, or O2). In some embodiments, a non-metallic element may form resistive material on a surface of the lithium metal. For example, LiCO3 or LiOH can create resistive losses for a lithium metal electrode. The presence of a non-metallic element can be detected using, for example, inductively coupled plasma optical emission spectroscopy (ICP-OES) or X- ray microtomography. The presence of a non-metallic elements may be detected using focused Ion Beam (FIB) with a secondary ion mass spectrometry (SIMS). The presence of a non-metallic elements may be detected using electron energy loss spectroscopy (EELS), and / or transmissionAtty Dkt No.: 65848-720601 electron microscopy (TEM), by detecting and mapping lithium via the high ionization cross- section of the shallow Li K-edge that is 10-100 times greater than those of other light elements, e.g., O and F.

[0386] Lithium metal can comprise less than 1500 ppm of a trace metal. Lithium metal can comprise less than 1400, 1300, 1200, 1100, 1000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of a trace metal. Lithium metal can comprise more than 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, or 5000 parts-per-billion (ppb) of a trace metal. The ppb can be by mass or by count. The ppb can correspond to a basis used for the instrument to detect the trace element. The trace metal can be aluminum, barium, calcium, chromium, iron, iridium, magnesium, tungsten, zinc, cobalt, or sodium. In some embodiments, a trace element may form an alloy with lithium. An alloy can reduce the capacity of a lithium metal electrode. Lithium metal can comprise less than 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of aluminum. Lithium metal can comprise less than 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of barium. Lithium metal can comprise less than 45, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of calcium. Lithium metal can comprise less than 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of chromium. Lithium metal can comprise less than 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of iron. Lithium metal can comprise less than 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of iridium. Lithium metal can comprise less than 1000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 5,040, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 ppm of magnesium. Lithium metal can comprise less than 23, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of tungsten. Lithium metal can comprise less than 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of zinc. Lithium metal can comprise less than 45, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of sodium. Lithium metal can comprise less than 45, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 ppm of cobalt. The presence of trace metals can be detected using, for example, inductively coupled plasma optical emission spectroscopy (ICP-OES).

[0387] Lithium metal can comprise a low density of structural impurities, e.g., subsurface structural impurities. Without being bound to a particular theory, elemental or molecular impurities in lithium metal may form phases which are distinct from a pure lithium phase. When current traverses through the lithium metal, the lithium metal may be heated. Higher temperature may permit impurities to conduct or diffuse in the lithium metal, which can lead to the formationAtty Dkt No.: 65848-720601 of more stable phases of impurities in the lithium metal (e.g., crystallites). When such structural impurities (phases which have distinct crystal structures, or which have grain boundaries against lithium metal phases in the lithium metal) begin to form, they may continue to grow. Structural impurities can be detected by 3D techniques, e.g., X-ray tomography. Structural impurities may be present on the surface of lithium metal, or it may be present beneath the surface. The structural impurities can provide sites for dendrite nucleation or growth, and may crack the surrounding lithium metal. In some embodiments, the lithium metal can comprise less than 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 structural impurities / mm3. In some embodiments, the lithium metal can comprise less than 1000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 5,040, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 ppm of structural impurities by weight. FABRICATION OF ETCHING-FREE CERAMIC ISLAND

[0388] As illustrated in FIG.39, a water-resistant polymer (e.g., COC) and ceramic powders (e.g., LICGC) are placed between elastic sheets (e.g., Teflon), forming a sandwich-like structure. This assembly is then hot-pressed using a spacer with the desired thickness. During the hot pressing, the water-resistant polymer melts, and the elastic sheet deforms, which facilitates the penetration of ceramic particles through the water-resistant polymer. However, since the elastic sheet remains intact and does not melt at this stage, the resulting ceramic island can be easily peeled off from the elastic sheet. An advantage of the process is that it eliminates the need for etching. In some embodiments, certain parameters including but not limited to the diameter of the ceramic particles, the thickness of the water-resistant polymer, the elastic sheet, and the spacer are pre-determined and optimized.

[0389] As illustrated in FIGs. 40-41, the ceramic island membrane can be made with multilayer polymer to be etch-free or to make etching more controllable. Polymer A, Polymer B, Polymer B' have different solubilities to organic solvent, or Polymer A is a chemically resistant polymer (e.g., PTFE). Polymer B and B’ is a water-resistant polymer (e.g., COC), or a Li+conductive polymer (e.g., PEG). Starting from multilayer polymer film, ceramic particles can be incorporated into the multilayer structure. Then, due to the difference in solubility, polymer B and polymer B' can be selectively and easily dissolved to form a conductive film without losing the water-protective effect of polymer A. When lithium-ion conductive polymer is used as Polymer B and Polymer B', nothing is required.Atty Dkt No.: 65848-720601

[0390] As illustrated in FIG.42, the ceramic island membrane can be fabricated using the combination of polymer A, polymer B, and adhesive tape. After pressing, the adhesive tape can be easily removed from the surface so that etching is only required on one side of the membrane. COMPUTING SYSTEM

[0391] In some aspects, the present disclosure describes a computer-implemented system comprising: a digital processing device comprising: at least one processor, an operating system configured to perform executable instructions, a memory, and a computer program including instructions executable by the digital processing device to manufacture a composite membrane, operate a system for extracting lithium from brine, or control a rechargeable energy source system. In some aspects, the present disclosure describes a computer-implemented method, implementing any one of the methods disclosed herein in a computer system. Referring to FIG. 14, a block diagram is shown depicting an exemplary machine that comprises a computer system 1500 (e.g., a processing or computing system) within which a set of instructions can execute for causing a device to perform or execute any one or more of the aspects and / or methodologies for manufacturing a composite membrane, operating a system for extracting lithium from brine, or controlling a rechargeable energy source system. The components in FIG.14 are examples only and do not limit the scope of use or functionality of any hardware, software, embedded logic component, or a combination of two or more such components implementing particular embodiments.

[0392] Computer system 1500 may comprise one or more processors 1501, a memory 1503, and a storage 1508 that communicate with each other, and with other components, via a bus 1540. The bus 1540 may also link a display 1532, one or more input devices 1533 (which may, for example, comprise a keypad, a keyboard, a mouse, a stylus, etc.), one or more output devices 1534, one or more storage devices 1535, and various tangible storage media 1536. All of these elements may interface directly or via one or more interfaces or adaptors to the bus 1540. For instance, the various tangible storage media 1536 can interface with the bus 1540 via storage medium interface 1526. Computer system 1500 may have any suitable physical form, including but not limited to one or more integrated circuits (ICs), printed circuit boards (PCBs), mobile handheld devices (such as mobile telephones or PDAs), laptop or notebook computers, distributed computer systems, computing grids, or servers.

[0393] Computer system 1500 comprises one or more processor(s) 1501 (e.g., central processing units (CPUs), general purpose graphics processing units (GPGPUs), or quantum processing units (QPUs)) that carry out functions. Computer system 1500 may be one of various highAtty Dkt No.: 65848-720601 performance computing platforms. For instance, the one or more processor(s) 1501 may form a high performance computing cluster. In some embodiments, the one or more processors 1501 may form a distributed computing system connected by wired and / or wireless networks. In some embodiments, arrays of CPUs, GPUs, QPUs, or any combination thereof may be operably linked to implement any one of the methods disclosed herein. Processor(s) 1501 optionally contains a cache memory unit 1502 for temporary local storage of instructions, data, or computer addresses. Processor(s) 1501 are configured to assist in execution of computer readable instructions. Computer system 1500 may provide functionality for the components depicted in FIG.14 as a result of the processor(s) 1501 executing non-transitory, processor-executable instructions embodied in one or more tangible computer-readable storage media, such as memory 1503, storage 1508, storage devices 1535, and / or storage medium 1536. The computer-readable media may store software that implements particular embodiments, and processor(s) 1501 may execute the software. Memory 1503 may read the software from one or more other computer-readable media (such as mass storage device(s) 1535, 1536) or from one or more other sources through a suitable interface, such as network interface 1520. The software may cause processor(s) 1501 to carry out one or more processes or one or more steps of one or more processes described or illustrated herein. Carrying out such processes or steps may comprise defining data structures stored in memory 1503 and modifying the data structures as directed by the software.

[0394] The memory 1503 may comprise various components (e.g., machine readable media) including, but not limited to, a random access memory component (e.g., RAM 1504) (e.g., static RAM (SRAM), dynamic RAM (DRAM), ferroelectric random access memory (FRAM), phase- change random access memory (PRAM), etc.), a read-only memory component (e.g., ROM 1505), and any combinations thereof. ROM 1505 may act to communicate data and instructions unidirectionally to processor(s) 1501, and RAM 1504 may act to communicate data and instructions bidirectionally with processor(s) 1501. ROM 1505 and RAM 1504 may comprise any suitable tangible computer-readable media described below. In one example, a basic input / output system 1506 (BIOS), including basic routines that help to transfer information between elements within computer system 1500, such as during start-up, may be stored in the memory 1503.

[0395] Fixed storage 1508 is connected bidirectionally to processor(s) 1501, optionally through storage control unit 1507. Fixed storage 1508 provides additional data storage capacity and may also comprise any suitable tangible computer-readable media described herein. Storage 1508 may be used to store operating system 1509, executable(s) 1510, data 1511, applications 1512 (application programs), and the like. Storage 1508 can also comprise an optical disk drive, aAtty Dkt No.: 65848-720601 solid-state memory device (e.g., flash-based systems), or a combination of any of the above. Information in storage 1508 may, in appropriate cases, be incorporated as virtual memory in memory 1503.

[0396] In one example, storage device(s) 1535 may be removably interfaced with computer system 1500 (e.g., via an external port connector (not shown)) via a storage device interface 1525. Particularly, storage device(s) 1535 and an associated machine-readable medium may provide non-volatile and / or volatile storage of machine-readable instructions, data structures, program modules, and / or other data for the computer system 1500. In one example, software may reside, completely or partially, within a machine-readable medium on storage device(s) 1535. In another example, software may reside, completely or partially, within processor(s) 1501.

[0397] Bus 1540 connects a wide variety of subsystems. Herein, reference to a bus may encompass one or more digital signal lines serving a common function, where appropriate. Bus 1540 may be any of several types of bus structures including, but not limited to, a memory bus, a memory controller, a peripheral bus, a local bus, and any combinations thereof, using any of a variety of bus architectures. As an example, and not by way of limitation, such architectures comprise an Industry Standard Architecture (ISA) bus, an Enhanced ISA (EISA) bus, a Micro Channel Architecture (MCA) bus, a Video Electronics Standards Association local bus (VLB), a Peripheral Component Interconnect (PCI) bus, a PCI-Express (PCI-X) bus, an Accelerated Graphics Port (AGP) bus, HyperTransport (HTX) bus, serial advanced technology attachment (SATA) bus, and any combinations thereof.

[0398] Computer system 1500 may also comprise an input device 1533. In one example, a user of computer system 1500 may enter commands and / or other information into computer system 1500 via input device(s) 1533. Examples of an input device(s) 1533 comprise, but are not limited to, an alpha-numeric input device (e.g., a keyboard), a pointing device (e.g., a mouse or touchpad), a touchpad, a touch screen, a multi-touch screen, a joystick, a stylus, a gamepad, an audio input device (e.g., a microphone, a voice response system, etc.), an optical scanner, a video or still image capture device (e.g., a camera), and any combinations thereof. In some embodiments, the input device is a Kinect, Leap Motion, or the like. Input device(s) 1533 may be interfaced to bus 1540 via any of a variety of input interfaces 1523 (e.g., input interface 1523) including, but not limited to, serial, parallel, game port, USB, FIREWIRE, THUNDERBOLT, or any combination of the above. In some embodiments, an input device 1533 may be used to manufacture a composite membrane, operate a system for extracting lithium from brine, orAtty Dkt No.: 65848-720601 control a rechargeable energy source system. In some embodiments, a computer-implemented method comprises using human inputs through an input device 1533.

[0399] In particular embodiments, when computer system 1500 is connected to network 1530, computer system 1500 may communicate with other devices, specifically mobile devices and enterprise systems, distributed computing systems, cloud storage systems, cloud computing systems, and the like, connected to network 1530. Communications to and from computer system 1500 may be sent through network interface 1520. For example, network interface 1520 may receive incoming communications (such as requests or responses from other devices) in the form of one or more packets (such as Internet Protocol (IP) packets) from network 1530, and computer system 1500 may store the incoming communications in memory 1503 for processing. Computer system 1500 may similarly store outgoing communications (such as requests or responses to other devices) in the form of one or more packets in memory 1503 and communicated to network 1530 from network interface 1520. Processor(s) 1501 may access these communication packets stored in memory 1503 for processing.

[0400] Examples of the network interface 1520 comprise, but are not limited to, a network interface card, a modem, and any combination thereof. Examples of a network 1530 or network segment 1530 comprise, but are not limited to, a distributed computing system, a cloud computing system, a wide area network (WAN) (e.g., the Internet, an enterprise network), a local area network (LAN) (e.g., a network associated with an office, a building, a campus or other relatively small geographic space), a telephone network, a direct connection between two computing devices, a peer-to-peer network, and any combinations thereof. A network, such as network 1530, may employ a wired and / or a wireless mode of communication. In general, any network topology may be used.

[0401] Information and data can be displayed through a display 1532. Examples of a display 1532 comprise, but are not limited to, a cathode ray tube (CRT), a liquid crystal display (LCD), a thin film transistor liquid crystal display (TFT-LCD), an organic liquid crystal display (OLED) such as a passive-matrix OLED (PMOLED) or active-matrix OLED (AMOLED) display, a plasma display, and any combinations thereof. The display 1532 can interface to the processor(s) 1501, memory 1503, and fixed storage 1508, as well as other devices, such as input device(s) 1533, via the bus 1540. The display 1532 is linked to the bus 1540 via a video interface 1522, and transport of data between the display 1532 and the bus 1540 can be controlled via the graphics control 1521. In some embodiments, the display is a video projector. In some embodiments, the display is a head-mounted display (HMD) such as a VR headset. In further embodiments, suitable VR headsets comprise, by way of non-limiting examples, HTC Vive,Atty Dkt No.: 65848-720601 Oculus Rift, Samsung Gear VR, Microsoft HoloLens, Razer OSVR, FOVE VR, Zeiss VR One, Avegant Glyph, Freefly VR headset, and the like. In still further embodiments, the display is a combination of devices such as those disclosed herein.

[0402] In addition to a display 1532, computer system 1500 may comprise one or more other peripheral output devices 1534 including, but not limited to, an audio speaker, a printer, a storage device, and any combinations thereof. Such peripheral output devices may be connected to the bus 1540 via an output interface 1524. Examples of an output interface 1524 comprise, but are not limited to, a serial port, a parallel connection, a USB port, a FIREWIRE port, a THUNDERBOLT port, and any combinations thereof.

[0403] In addition, or as an alternative, computer system 1500 may provide functionality as a result of logic hardwired or otherwise embodied in a circuit, which may operate in place of or together with software to execute one or more processes or one or more steps of one or more processes described or illustrated herein. Reference to software in this disclosure may encompass logic, and reference to logic may encompass software. Moreover, reference to a computer- readable medium may encompass a circuit (such as an IC) storing software for execution, a circuit embodying logic for execution, or both, where appropriate. The present disclosure encompasses any suitable combination of hardware, software, or both.

[0404] Those of skill in the art will appreciate that the various illustrative logical blocks, modules, circuits, and algorithm steps described in connection with the embodiments disclosed herein may be implemented as electronic hardware, computer software, or combinations of both. To clearly illustrate this interchangeability of hardware and software, various illustrative components, blocks, modules, circuits, and steps have been described above generally in terms of their functionality.

[0405] The various illustrative logical blocks, modules, and circuits described in connection with the embodiments disclosed herein may be implemented or performed with a general purpose processor, a digital signal processor (DSP), an application specific integrated circuit (ASIC), a field programmable gate array (FPGA) or other programmable logic device, discrete gate or transistor logic, discrete hardware components, or any combination thereof designed to perform the functions described herein. A general purpose processor may be a microprocessor, but in the alternative, the processor may be any conventional processor, controller, microcontroller, or state machine. A processor may also be implemented as a combination of computing devices, e.g., a combination of a DSP and a microprocessor, a plurality of microprocessors, one or more microprocessors in conjunction with a DSP core, or any other such configuration.Atty Dkt No.: 65848-720601

[0406] The steps of a method or algorithm described in connection with the embodiments disclosed herein may be embodied directly in hardware, in a software module executed by one or more processor(s), or in a combination of the two. A software module may reside in RAM memory, flash memory, ROM memory, EPROM memory, EEPROM memory, registers, hard disk, a removable disk, a CD-ROM, or any other form of storage medium known in the art. An exemplary storage medium is coupled to the processor such the processor can read information from, and write information to, the storage medium. In the alternative, the storage medium may be integral to the processor. The processor and the storage medium may reside in an ASIC. The ASIC may reside in a user terminal. In the alternative, the processor and the storage medium may reside as discrete components in a user terminal.

[0407] In accordance with the description herein, suitable computing devices comprise, by way of non-limiting examples, server computers, desktop computers, laptop computers, notebook computers, sub-notebook computers, netbook computers, netpad computers, set-top computers, media streaming devices, handheld computers, Internet appliances, mobile smartphones, and tablet computers.

[0408] In some embodiments, the computing device comprises an operating system configured to perform executable instructions. The operating system is, for example, software, including programs and data, which manages the device’s hardware and provides services for execution of applications. Those of skill in the art will recognize that suitable server operating systems comprise, by way of non-limiting examples, FreeBSD, OpenBSD, NetBSD®, Linux, Apple®Mac OS X Server®, Oracle®Solaris®, Windows Server®, and Novell®NetWare®. Those of skill in the art will recognize that suitable personal computer operating systems comprise, by way of non-limiting examples, Microsoft®Windows®, Apple®Mac OS X®, UNIX®, and UNIX-like operating systems such as GNU / Linux®. In some embodiments, the operating system is provided by cloud computing. Those of skill in the art will also recognize that suitable mobile smartphone operating systems comprise, by way of non-limiting examples, Nokia®Symbian®OS, Apple®Ios®, Research In Motion®BlackBerry OS®, Google®Android®, Microsoft®Windows Phone®OS, Microsoft®Windows Mobile®OS, Linux®, and Palm®WebOS®.

[0409] In some embodiments, a computer system 1500 may be accessible through a user terminal to receive user commands. The user commands may comprise line commands, scripts, programs, etc., and various instructions executable by the computer system 1500. A computer system 1500 may receive instructions to manufacture a composite membrane, operate a system for extracting lithium from brine, or control a rechargeable energy source system, or to schedule a computing job for the computer system 1500 to carry out any instructions.Atty Dkt No.: 65848-720601 NON-TRANSITORY COMPUTER READABLE STORAGE MEDIUM

[0410] In some aspects, the present disclosure describes a non-transitory computer-readable storage media encoded with a computer program including instructions executable by one or more processors to manufacture a composite membrane, operate a system for extracting lithium from brine, or control a rechargeable energy source system using any one of the methods disclosed herein. In some embodiments, a non-transitory computer-readable storage media may comprise instructions for manufacturing a composite membrane, operating a system for extracting lithium from brine, or controlling a rechargeable energy source system. In some embodiments, the platforms, systems, media, and methods disclosed herein comprise one or more non-transitory computer readable storage media encoded with a program including instructions executable by the operating system of an optionally networked computing device.

[0411] In further embodiments, a computer readable storage medium is a tangible component of a computing device. In still further embodiments, a computer readable storage medium is optionally removable from a computing device. In some embodiments, a computer readable storage medium comprises, by way of non-limiting examples, flash memory devices, solid state memory, magnetic disk drives, magnetic tape drives, optical disk drives, distributed computing systems including cloud computing systems and services, and the like. In some embodiments, the program and instructions are permanently, substantially permanently, semi-permanently, or non-transitorily encoded on the media. COMPUTER PROGRAM

[0412] In some aspects, the present disclosure describes a computer program product comprising a computer-readable medium having computer-executable code encoded therein, the computer- executable code adapted to be executed to implement any one of the methods disclosed herein. In some embodiments, the platforms, systems, media, and methods disclosed herein comprise at least one computer program, or use of the same.

[0413] A computer program comprises a sequence of instructions, executable by one or more processor(s) of the computing device’s CPU, written to perform a specified task. Computer readable instructions may be implemented as program modules, such as functions, objects, Application Programming Interfaces (APIs), computing data structures, and the like, that perform particular tasks or implement particular abstract data types. In light of the disclosure provided herein, those of skill in the art will recognize that a computer program may be written in various versions of various languages. In some embodiments, APIs may comprise variousAtty Dkt No.: 65848-720601 languages, for example, languages in various releases of TensorFlow, Theano, Keras, PyTorch, or any combination thereof which may be implemented in various releases of Python, Python3, C, C#, C++, MatLab, R, Java, or any combination thereof.

[0414] The functionality of the computer readable instructions may be combined or distributed as desired in various environments. In some embodiments, a computer program comprises one sequence of instructions. In some embodiments, a computer program comprises a plurality of sequences of instructions. In some embodiments, a computer program is provided from one location. In other embodiments, a computer program is provided from a plurality of locations. In various embodiments, a computer program comprises one or more software modules. In various embodiments, a computer program comprises, in part or in whole, one or more web applications, one or more standalone applications, one or more web browser plug-ins, extensions, add-ins, or add-ons, or combinations thereof. WEB APPLICATION

[0415] In some embodiments, a computer program comprises a web application. In some embodiments, a user may enter a query for manufacturing a composite membrane, operating a system for extracting lithium from brine, or controlling a rechargeable energy source system through a web application. In light of the disclosure provided herein, those of skill in the art will recognize that a web application, in various embodiments, utilizes one or more software frameworks and one or more database systems. In some embodiments, a web application is created upon a software framework such as Microsoft®.NET or Ruby on Rails (RoR). In some embodiments, a web application utilizes one or more database systems including, by way of non- limiting examples, relational, non-relational, object oriented, associative, XML, and document oriented database systems. In further embodiments, suitable relational database systems comprise, by way of non-limiting examples, Microsoft®SQL Server, mySQL™, and Oracle®. Those of skill in the art will also recognize that a web application, in various embodiments, is written in one or more versions of one or more languages. A web application may be written in one or more markup languages, presentation definition languages, client-side scripting languages, server-side coding languages, database query languages, or combinations thereof. In some embodiments, a web application is written to some extent in a markup language such as Hypertext Markup Language (HTML), Extensible Hypertext Markup Language (XHTML), or eXtensible Markup Language (XML). In some embodiments, a web application is written to some extent in a presentation definition language such as Cascading Style Sheets (CSS). In some embodiments, a web application is written to some extent in a client-side scripting language suchAtty Dkt No.: 65848-720601 as Asynchronous JavaScript and XML (AJAX), Flash®ActionScript, JavaScript, or Silverlight®. In some embodiments, a web application is written to some extent in a server-side coding language such as Active Server Pages (ASP), ColdFusion®, Perl, Java™, JavaServer Pages (JSP), Hypertext Preprocessor (PHP), Python™, Ruby, Tcl, Smalltalk, WebDNA®, or Groovy. In some embodiments, a web application is written to some extent in a database query language such as Structured Query Language (SQL). In some embodiments, a web application integrates enterprise server products such as IBM®Lotus Domino®. Mobile application

[0416] In some embodiments, a computer program comprises a mobile application provided to a mobile computing device. In some embodiments, the mobile application is provided to a mobile computing device at the time it is manufactured. In other embodiments, the mobile application is provided to a mobile computing device via the computer network described herein.

[0417] In view of the disclosure provided herein, a mobile application is created by techniques known to those of skill in the art using hardware, languages, and development environments known to the art. Those of skill in the art will recognize that mobile applications are written in several languages. Suitable programming languages comprise, by way of non-limiting examples, C, C++, C#, Objective-C, Java™, JavaScript, Pascal, Object Pascal, Python™, Ruby, VB.NET, WML, and XHTML / HTML with or without CSS, or combinations thereof.

[0418] Suitable mobile application development environments are available from several sources. Commercially available development environments comprise, by way of non-limiting examples, AirplaySDK, alcheMo, Appcelerator®, Celsius, Bedrock, Flash Lite, .NET Compact Framework, Rhomobile, and WorkLight Mobile Platform. Other development environments are available without cost including, by way of non-limiting examples, Lazarus, MobiFlex, MoSync, and Phonegap. Also, mobile device manufacturers distribute software developer kits including, by way of non-limiting examples, iPhone and iPad (Ios) SDK, Android™ SDK, BlackBerry®SDK, BREW SDK, Palm®OS SDK, Symbian SDK, webOS SDK, and Windows®Mobile SDK. Standalone application

[0419] In some embodiments, a computer program comprises a standalone application, which is a program that is run as an independent computer process, not an add-on to an existing process, e.g., not a plug-in. Those of skill in the art will recognize that standalone applications are often compiled. A compiler is a computer program(s) that transforms source code written in aAtty Dkt No.: 65848-720601 programming language into binary object code such as assembly language or machine code. Suitable compiled programming languages comprise, by way of non-limiting examples, C, C++, Objective-C, COBOL, Delphi, Eiffel, Java™, Lisp, Python™, Visual Basic, and VB .NET, or combinations thereof. Compilation is often performed, at least in part, to create an executable program. In some embodiments, a computer program comprises one or more executable complied applications. SOFTWARE MODULES

[0420] In some embodiments, the platforms, systems, media, and methods disclosed herein comprise software, server, and / or database modules, or use of the same. In view of the disclosure provided herein, software modules are created by techniques known to those of skill in the art using machines, software, and languages known to the art. The software modules disclosed herein are implemented in a multitude of ways. In various embodiments, a software module comprises a file, a section of code, a programming object, a programming structure, a distributed computing resource, a cloud computing resource, or combinations thereof. In further various embodiments, a software module comprises a plurality of files, a plurality of sections of code, a plurality of programming objects, a plurality of programming structures, a plurality of distributed computing resources, a plurality of cloud computing resources, or combinations thereof. In various embodiments, the one or more software modules comprise, by way of non-limiting examples, a web application, a mobile application, a standalone application, and a distributed or cloud computing application. In some embodiments, software modules are in one computer program or application. In other embodiments, software modules are in more than one computer program or application. In some embodiments, software modules are hosted on one machine. In other embodiments, software modules are hosted on more than one machine. In further embodiments, software modules are hosted on a distributed computing platform such as a cloud computing platform. In some embodiments, software modules are hosted on one or more machines in one location. In other embodiments, software modules are hosted on one or more machines in more than one location. LIST OF EMBODIMENTS

[0421] The following list of embodiments of the invention are to be considered as disclosing various features of the invention, which features can be considered to be specific to the particular embodiment under which they are discussed, or which are combinable with the various otherAtty Dkt No.: 65848-720601 features as listed in other embodiments. Thus, simply because a feature is discussed under one particular embodiment does not necessarily limit the use of that feature to that embodiment.

[0422] Embodiment 1. A system for extracting lithium metal from a brine comprising: (a) an anode, disposed in the brine; (b) a solution of an organic solvent having as dissolved solutes a coordination compound, and a lithium salt, i. wherein the solution is in contact with the brine, ii. wherein the organic solvent is insoluble in the brine, and iii. wherein the coordination compound selectively coordinates lithium cation in preference to other cations; and (c) an electrically conductive substrate, in contact with the solution, but physically separated from the brine, (d) wherein the system is configured so that when voltage is applied across the anode and the electrically conductive substrate, lithium cation is extracted from the brine and a layer of lithium metal or lithium metal alloy is deposited on a surface of the electrically conductive substrate.

[0423] Embodiment 2. The system for extracting lithium metal from the brine of Embodiment 1, wherein the coordination compound, and the lithium salt are insoluble in the brine. Embodiment 3. The system for extracting lithium metal from the brine of Embodiment 1 or 2, wherein the coordination compound is a lithium ion selective clathrate.

[0424] Embodiment 4. The system for extracting lithium metal from the brine of Embodiment 3, wherein the clathrate is selected from the group consisting of a crown ether, a nitrogen- containing cryptand, and an orthoester cryptand.

[0425] Embodiment 5. The system for extracting metal from the brine of Embodiment 3 or 4, wherein the clathrate is a crown ether.

[0426] Embodiment 6. The system for extracting lithium metal from the brine of Embodiment 5, wherein the lithium ion selective crown ether is selected from the group consisting of 14-crown- 4, substituted derivatives of 14-crown-4, 12-crown-4, substituted derivatives of 12-crown-4, 15- crown-5, substituted derivatives of 15-crown-5, and combinations thereof.

[0427] Embodiment 7. The system for extracting lithium metal from the brine of any one of Embodiments 1-6, wherein the lithium salt comprises an anion with a chemical structure of (RS(O)2)2N-, where R is a substituent selected from the group of alkyl, perfluorinated alkyl, partially fluorinated alkyl, aryl, perfluorinated aryl, partially fluorinated aryl, and combinations thereof.

[0428] Embodiment 8. The system for extracting lithium metal from the brine of any one of Embodiments 1-7, wherein the organic solvent is selected from the group consisting of CH3(CH2)pO[(CH2)qOCH2(CF2)nCH2O]x(CH2)rCH3 (n = 1-15, p = 0-15, q = 0-15, r = 0-15, x = 1-30), alkanes, and combinations thereof.Atty Dkt No.: 65848-720601

[0429] Embodiment 9. A method of extracting lithium metal from a brine, comprising the steps of (a) disposing an anode in the brine; (b) placing a solution in contact with the brine, the solution comprising an organic solvent and having as dissolved solutes a coordination compound and a lithium salt, wherein the organic solvent, the coordination compound, and the lithium salt are insoluble in the brine, and wherein the coordination compound selectively coordinates lithium cation in preference to other cations; (c) disposing an electrically conductive substrate to be in contact with the solution, but physically separated from the brine; and (d) applying voltage across the anode and the electrically conductive substrate, thereby causing a layer of lithium metal or lithium metal alloy to be deposited on a surface of the electrically conductive substrate.

[0430] Embodiment 10. The method of Embodiment 9, further comprising (a) removing the layer of lithium metal or lithium metal alloy from contact with the brine and cleaning a surface of the layer of lithium metal or lithium metal alloy.

[0431] Embodiment 11. The method of Embodiment 10, wherein the cleaning includes contacting with an organic solvent.

[0432] Embodiment 12. The method of Embodiment 11, wherein the organic solvent is hexane or dimethyl carbonate.

[0433] Embodiment 13. The method of Embodiment 11 or 12, wherein contacting with an organic solvent includes operations selected from the group of soaking, rinsing, and combinations thereof.

[0434] Embodiment 14. The method of any one of Embodiments 11-13, wherein the cleaning includes brushing with a soft sponge and sonication in the organic solvent.

[0435] Embodiment 15. A system for extracting one or more metals from a brine comprising: (a) an anode, disposed in the brine; (b) an organic solution comprising an organic solvent and having as dissolved solutes one or more coordination compounds, and salts of the one or more metals, (i) wherein the organic solution is in contact with the brine, (ii) wherein the organic solvent, the one or more coordination compounds, and the salts of the one or more metals are insoluble in the brine, and (iii) wherein the one or more coordination compounds are configured to coordinate cations of the one or more metals; and (c) an electrically conductive substrate, in contact with the organic solution, but physically separated from the brine, (d) wherein the system is configured so that when voltage is applied across the anode and the electrically conductive substrate, cations of the one or more metals are extracted from the brine and a layer of a metal or metal alloy is deposited on a surface of the electrically conductive substrate.

[0436] Embodiment 16. The system for extracting one or more metals from a brine according to Embodiment 15, wherein the one or more coordination compounds are configured to selectivelyAtty Dkt No.: 65848-720601 coordinate specific metal cations, thereby providing a means of controlling the composition of the layer of metal or metal alloy.

[0437] Embodiment 17. A method for extracting lithium from an aqueous lithium resource, comprising: (a) transporting lithium ions from the aqueous lithium resource to a non-aqueous electrolyte comprising one or more coordination compounds, wherein the one or more coordination compounds coordinate with the lithium ions; (b) transporting the lithium ions coordinated by the one or more coordination compounds from the non-aqueous electrolyte to a substrate; and (c) electrodepositing lithium metal on the substrate by reducing the lithium ions to the lithium metal.

[0438] Embodiment 18. The method of Embodiment 17, wherein the one or more coordination compounds are substantially insoluble in the aqueous lithium resource.

[0439] Embodiment 19. The method of Embodiment 17 or 18, wherein water in the aqueous lithium resource is insoluble in the non-aqueous electrolyte.

[0440] Embodiment 20. The method of any one of Embodiments 17-19, wherein the non- aqueous electrolyte comprises an organic solvent.

[0441] Embodiment 21. The method of Embodiment 20, wherein the organic solvent comprises a molecule comprising one or more carbon-fluorine bonds.

[0442] Embodiment 22. The method of any one of Embodiments 17-21, wherein the non- aqueous electrolyte comprises a lithium salt.

[0443] Embodiment 23. The method of Embodiment 22, wherein the lithium salt is substantially insoluble in the organic solvent in the absence of the one or more coordination compounds.

[0444] Embodiment 24. The method of any one of Embodiments 17-23, wherein the one or more coordination compounds selectively coordinate with the lithium ions.

[0445] Embodiment 25. The method of any one of Embodiments 17-24, wherein the one or more coordination compounds preferentially coordinate with the lithium ions over non-lithium cations.

[0446] Embodiment 26. The method of Embodiment 25, wherein the non-lithium cations comprises any one of sodium, potassium, magnesium, calcium, and any combination thereof.

[0447] Embodiment 27. The method of any one of Embodiments 17-26, wherein the one or more coordination compounds comprise a plurality of ether groups, wherein oxygen atoms of the plurality of ether groups coordinate with the lithium ions.

[0448] Embodiment 28. The method of Embodiment 27, wherein the one or more coordination compounds comprise one or more crown ethers.Atty Dkt No.: 65848-720601

[0449] Embodiment 29. The method of any one of Embodiments 17-28, wherein the one or more coordination compounds comprise a plurality of amine groups, wherein nitrogen atoms of the plurality of amine groups coordinate with the lithium ions.

[0450] Embodiment 30. The method of Embodiment 29, wherein the one or more coordination compounds comprise one or more cryptands. Embodiment 31. The method of any one of Embodiments 17-30, wherein the one or more coordination compounds comprise any one of lariat ethers, multi-armed ethers, calixarenes, spherands, cryptaspherand, hemispherand, podand, and any combination thereof.

[0451] Embodiment 32. The method of any one of Embodiments 17-31, wherein the aqueous lithium resource comprises sodium, potassium, magnesium, calcium, boron, chlorine, SO42-, nitrogen, an alkali metal, an alkali earth metal, or any combination thereof.

[0452] Embodiment 33. The method of Embodiment 32, wherein a ratio of magnesium to lithium in the aqueous lithium resource is about 0-100 by mass or by mols.

[0453] Embodiment 34. The method of any one of Embodiments 17-33, wherein the aqueous lithium resource comprises a geological resource.

[0454] Embodiment 35. The method of Embodiment 34, wherein the aqueous lithium resource comprises brine.

[0455] Embodiment 36. The method of Embodiment 34 or 35, wherein the aqueous lithium resource is pretreated by dilution, concentration, filtration, nanofiltration, absorption or extraction using organic molecules or inorganic sorbents, electrodialysis using a membrane, concentration and precipitation, solvent extraction, pH adjustment, or any combination thereof.

[0456] Embodiment 37. The method of Embodiment 35, wherein the pH adjustment comprises adding an acid, a base, a buffer, or any combination thereof.

[0457] Embodiment 38. The method of Embodiment 36 or 37, wherein the pretreatment removes magnesium in the aqueous lithium resource.

[0458] Embodiment 39. The method of any one of Embodiments 17-38, wherein the substrate comprises copper.

[0459] Embodiment 40. The method of any one of Embodiments 17-39, wherein the lithium metal comprises less than 0.1 wt% or at% of nitrogen, oxygen, or both.

[0460] Embodiment 4...

Claims

Atty Dkt No.: 65848-720601 CLAIMS What is claimed is:

1. A method for electrochemically extracting lithium from a lithium resource, comprising: (a) contacting an electrochemical cell with the lithium resource, wherein the electrochemical cell comprises an electrolyte, and the lithium resource comprises water; (b) depositing lithium on an electrode of the electrochemical cell by applying a voltage across the electrolyte; and (c) dehydrating the electrolyte to maintain water content in the electrolyte below a predetermined threshold.

2. The method of claim 1, wherein the dehydrating in (c) is performed separately from the depositing in (b).

3. The method of claim 1, wherein the dehydrating in (c) occurs at a different location from the depositing in (b).

4. The method of claim 1, wherein the dehydrating in (c) is performed in a chamber that is separated from a chamber performing the depositing in (b).

5. The method of claim 1, wherein the dehydrating in (c) is performed in the same chamber as the depositing in (b).

6. The method of claim 1, wherein the dehydrating in (c) comprises evaporating and / or boiling water in the electrolyte.

7. The method of claim 1, wherein the dehydrating in (c) comprises applying at least one of heat or vacuum to the electrolyte.

8. The method of claim 1, wherein the dehydrating in (c) comprises bubbling gas through the electrolyte, wherein the gas comprises a temperature higher than the electrolyte.

9. The method of claim 1, wherein the dehydrating in (c) comprises electrolyzing water in the electrolyte.

10. The method of claim 1, wherein the dehydrating in (c) comprises contacting the electrolyte with an adsorbent or an absorbent to remove water from the electrolyte.

11. The method of claim 1, wherein the predetermined threshold is 1000, 100, 50, or 10 ppm of water as determined using 1H NMR, Karl Fischer titration, or NIR spectroscopy.

12. The method of claim 1, wherein the electrolyte is removed from the electrochemical cell prior to the dehydrating in (c).Atty Dkt No.: 65848-720601 13. The method of claim 1, wherein the dehydrating in (c) is performed after the depositing in (b).

14. The method of claim 13, further comprising depositing the lithium on a second electrode of the electrochemical cell by applying a voltage between the Li deposition substrate and the counter electrode in the lithium resource.

15. The method of claim 14, wherein the electrode is in the electrolyte, and the counter electrode is in the lithium resource.

16. The method of claim 1, wherein the lithium resource comprises sodium, potassium, magnesium, calcium, boron, chlorine, SO42-, nitrogen, an alkali metal, an alkali earth metal, or any combination thereof.

17. The method of claim 1, wherein a ratio of magnesium to lithium in the lithium resource is about 0-1000.

18. The method of claim 1, wherein the lithium resource comprises an aqueous solution of metal salts comprising (i) a lithium salt and (ii) a sodium salt, a magnesium salt, a calcium salt, a potassium salt, or any combination thereof.

19. The method of claim 1, wherein the electrolyte comprises a vapor pressure of less than 0.1, 0.01, or 0.001 hPa at 20 °C.

20. The method of claim 1, wherein the lithium resource or the electrolyte comprises an additive, wherein the additive is configured to bind with lithium ions in the lithium resource preferentially over the lithium ions binding with water 21. The method of claim 20, wherein the additive forms molecular cages around lithium ions.

22. The method of claim 21, wherein the additive comprises a coordination compound.

23. A system for electrochemically extracting lithium from a lithium resource, comprising: (a) an electrochemical cell comprising an electrolyte, wherein the electrochemical cell is configured to contact with the lithium resource; (b) a power source configured to apply a current across the electrolyte; and (c) a dehydrator configured to dehydrate the electrolyte to maintain water content in the electrolyte below a predetermined threshold.

24. A lithium conductive membrane comprising: a. a polymer comprising a hydrophobic repeating unit and a coordination chemistry, and wherein the coordination chemistry is configured to coordinate with lithium ions; and b. the lithium ions;Atty Dkt No.: 65848-720601 wherein the lithium conductive membrane is configured to provide a water permeability of less than 1.0 g / m2･day as measured at least in part by Near-Infrared (NIR) spectroscopy, and wherein the lithium conductive membrane is configured to provide a Li+conductivity of at least about 1.0 × 10-6S / cm at room temperature through the lithium conductive membrane.

25. A flexible conductive composite membrane comprising: a hydrophobic film layer and one or more lithium ion conductive particles, wherein the composite membrane is substantially impermeable to water and is configured to provide a Li+conductivity of at least about 1.0 × 10-5S / cm through the composite membrane.

26. A rechargeable energy source system comprising: a composite membrane comprising a hydrophobic film layer and one or more lithium ion conductive particles, wherein the one or more lithium ion conducting particles each provide an exposed particle surface on two sides of the hydrophobic film layer, wherein the composite membrane is substantially impermeable to water when the rechargeable energy source system is in operation or not in operation.

27. A method of operating a rechargeable energy source system, comprising: depositing lithium from a cathode at an anode through a composite membrane comprising a hydrophobic film layer and one or more lithium ion conductive particles, wherein the one or more lithium ion conducting particles each provide an exposed particle surface on two sides of the hydrophobic film layer, wherein the depositing of the lithium at the anode is substantially free of side reactions caused by water and / or other impurities.

28. A system for lithium extraction from brine comprising: a composite membrane comprising a hydrophobic film layer and one or more lithium ion conductive particles, wherein the composite membrane is substantially impermeable to water when the system for lithium extraction is in operation or not in operation.

29. A method of operating a system for lithium extraction from brine, comprising: depositing lithium from a lithium metal anode at a cathode through a composite membrane comprising a hydrophobic film layer and one or more lithium ion conductive particles,Atty Dkt No.: 65848-720601 wherein the depositing of the lithium at the cathode is substantially free of side reactions caused by water and / or other impurities.

Images