Method for producing lithium metal or alloy thereof or for prelithizing electrode materials

Abstract

The invention relates to a re-lithiated lithium intercalation material for producing lithium metal or for pre-lithiating an electrode material, and to an anode and a production cell comprising such a material. The invention also relates to a method for producing lithium metal and for pre-lithiating an electrode material. The method comprises performing an electrolytic reaction for producing lithium in the electrolytic cell, wherein the electrolytic cell comprises the re-lithiated lithium intercalation material as an anode, a current collector as a cathode, and an electrolyte comprising a lithium salt.

Description

Technical Field

[0001] The present invention relates to a method for producing lithium metal or its alloys or pre-lithiating electrode materials. More specifically, the present invention relates to a method for producing lithium metal or its alloys in some cases and pre-lithiating electrode materials in other cases, all from relithiating lithium intercalation materials. Background Art

[0002] Lithium metal is traditionally produced by electrolyzing LiCl in a molten salt medium at very high temperatures (typically between 400°C and 450°C). The electrolyte consists of a mixture of LiCl and KCl, which forms a eutectic with a melting point of 355°C and a composition of 45% LiCl and 55% KCl. This electrolyte is chemically resistant to the chlorine gas released by the anode during electrolysis and also enables the realization of several thousand A / m 2 The current density of the order of magnitude. However, despite the high production rate of the production cell, the method has several disadvantages. The electrolysis must be carried out at very high temperatures. The anode reaction involves the release of chlorine, which is highly corrosive (especially at high temperatures). In addition, the lithium metal produced is in liquid form at these high temperatures, which makes it more complicated to handle due to its high reactivity in liquid form. The combination of high temperatures and the handling of corrosive chlorine and highly reactive liquid lithium metal leads to high investment and operating costs for this traditional lithium metal production method. Another disadvantage of this method is that in the case of manufacturing lithium batteries based on lithium metal foil used as anode material, it is necessary to use several extrusion and rolling steps to process the resulting lithium metal ingot into thin foil, which increases investment and operating costs.

[0003] To reduce the electrolysis temperature and avoid handling liquid lithium metal, lithium electrodeposition in room temperature ionic liquids (RTILs) has been proposed. However, the proposed method does not address the issue of an anodic reaction that does not lead to degradation of the electrolytic medium.

[0004] It has been proposed to use lithium metal as an anode material in order to avoid electrolyte degradation during the anodic reaction during the electrodeposition of lithium metal. This approach has been applied to both the production of lithium thin films on current collectors and the pre-lithiation of anode materials such as graphite, silicon, etc. However, this relies on the oxidation of lithium as a compatible anodic reaction and still involves the use of lithium metal produced using traditional high-temperature methods using LiCl as a starting material.

[0005] Bodoin et al. (US2022 / 0367874A1) and Kang et al. (2021 / 0381115A1) have proposed the use of an electrolytic cell with a lithium-selective ceramic membrane that separates an anode compartment containing an aqueous solution of a lithium salt from a cathode compartment containing an organic solvent and another lithium salt. This method has several advantages, namely that an anodic reaction that is incompatible with the electrolytic medium is avoided (in this case, the anodic reaction is the release of oxygen in the aqueous medium), the electrolysis is carried out at low temperatures, and the raw material for producing lithium metal can be any lithium salt, such as lithium carbonate. In addition, the proposed method also has several important disadvantages, such as the use of expensive and fragile ceramic membranes, and water molecules leak through the ceramic membrane into the organic electrolyte, and thus cause the lithium metal to be contaminated with LiOH.

[0006] On another topic, next-generation energy storage technologies require advanced active electrode materials with improved gravimetric and volumetric capabilities to achieve enhanced gravimetric and volumetric energy density. However, most of these materials suffer from high first-cycle loss of active lithium, for example due to the formation of a solid electrolyte interphase (SEI), which has so far hindered their widespread commercial application. Indeed, when a battery is first charged, a certain amount of active lithium is lost, reducing the remaining active lithium content. Typically, this loss of active lithium permanently reduces the available energy due to this consumption of lithium by the electrode material. Prelithiation is considered a highly attractive technique to compensate for this loss of active lithium and, therefore, to improve practical energy density. Prelithiation involves the addition / doping of lithium to battery electrodes before operating the battery cell. Prelithiation can effectively compensate for lithium loss during the first cycle and improve initial coulombic efficiency. It is a versatile approach that can be applied to a variety of electrode materials and improve battery performance. To date, various prelithiation techniques have been evaluated, including electrochemical and chemical prelithiation, prelithiation using additives, or even prelithiation via direct contact with lithium metal.

[0007] In the case of electrochemical pre-lithiation methods, the lithium source consists of a lithium metal electrode coupled to a lithium intercalation material. When an electric current is applied, the lithium metal oxidizes and migrates to the counter electrode, where it is intercalated into the lithium intercalation material. Park et al. (WO 2019 / 113534 A1) applied this method to the pre-lithiation of silicone intercalation materials. In this patent application, the use of a lithium metal counter electrode increases costs and still involves the above-mentioned issues regarding the use of highly active lithium metal.

[0008] In order to avoid the problems associated with using lithium metal as a lithium source for pre-lithiation, Grant et al. (US 9 598 789 B2) have developed a method for pre-lithiation of the anode using a lithium salt (i.e., LiCl) dissolved in the electrolyte as the lithium source. In this patent, the lithium metal counter electrode is replaced by an inert metal foil, where anolyte degradation reactions such as the release of chlorine are expected to occur. This system is conducive to degradation of the electrolyte salt, high power consumption, and limited current density. Summary of the Invention

[0009] According to the present invention, the following is provided:

[0010] 1. A relithiated lithium intercalation material for producing lithium metal or its alloys or for prelithiating electrode materials.

[0011] 2. Use of a relithiated lithium intercalation material for producing lithium metal or its alloys or for prelithiating electrode materials.

[0012] 3. The material / use according to Example 1 or Example 2, which is used to produce the lithium metal or its alloy, preferably to produce the lithium metal, preferably wherein the lithium metal or its alloy is in the form of a film, preferably wherein the lithium metal or its alloy is produced by electrodeposition.

[0013] 4. The material / use according to embodiment 1 or embodiment 2, wherein the material / use is used to pre-lithiate an electrode material, preferably to pre-lithiate an anode material, more preferably to pre-lithiate graphite, silicon, silicon oxide (SiO x ), pre-lithiation of silicon-carbon composite materials, carbon nanotubes or their mixtures.

[0014] 5. The material / use according to any one of embodiments 1 to 4, wherein the relithiated lithium intercalation material is lithium phosphate or lithium oxide, preferably:

[0015] ·Li w FePO4 (wherein w≤1.1, preferably w is 1),

[0016] ·Li w Fe 1-x Mn x PO4 (wherein w≤1.1, preferably w is 1; 0<x≤1, preferably 0.2 <x≤0.4),

[0017] ·Li w Mn2O4 (wherein w≤1.1, preferably w is 1),

[0018] ·Li w Mn 1.5 Ni 0.5O4 (where w ≤ 1.1, preferably w is 1),

[0019] ·Li 4+z Ti5O 12 (where 0 < z ≤ 3), or

[0020] ·NMC (Li w Ni 1-x-y Mn x Co y O2, where w ≤ 1.3, preferably w is 1; 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, and 0 ≤ z ≤ 1, and M is aluminum, magnesium, titanium, niobium, zirconium, tungsten, molybdenum, yttrium, lanthanum, tantalum or a mixture thereof).

[0021] 6. The material / use according to embodiment 5, wherein the relithiated lithium intercalation material is Li w FePO4.

[0022] 7. The material / use according to any one of embodiments 1 to 6, wherein the relithiated lithium intercalation material has been obtained from a used electrode and then relithiated, or wherein the relithiated lithium intercalation material has been used to produce lithium metal or its alloy or to prelithiate an electrode material and then relithiated.

[0023] 8. The material / use according to any one of embodiments 1 to 7, wherein the relithiated lithium intercalation material has recovered at least 50%, preferably at least 75%, more preferably at least 85%, even more preferably at least 95% and most preferably still at least 99% of the previously deintercalated lithium ions.

[0024] 9. A production anode for producing lithium metal or its alloy or for prelithiating an electrode material, the production anode comprising a relithiated lithium intercalation material.

[0025] 10. Use of a production anode comprising a relithiated lithium intercalation material for producing lithium metal or its alloy or for prelithiating an electrode material.

[0026] 11. The production anode / use according to embodiment 9 or embodiment 10, wherein the relithiated lithium intercalation material is defined as in any one of embodiments 1 to 8.

[0027] 12. The production anode / use according to any one of claims 9 to 11, the production anode / use being intended for producing the lithium metal or the alloy thereof, preferably intended for producing lithium metal, preferably wherein the lithium metal or the alloy thereof is in the form of a film, preferably wherein the lithium metal or the alloy thereof is produced by electrodeposition.

[0028] 13. The production anode / use according to embodiment 12, wherein the anode is intended to perform an electrolysis reaction for producing lithium.

[0029] 14. The production anode / use according to embodiment 12 or embodiment 13, wherein the production anode further comprises a current collector, and the relithiated lithium intercalation material is deposited on the current collector.

[0030] 15. Production of an anode / use according to embodiment 14, wherein the current collector is a metal foil, preferably made of copper, aluminum, stainless steel, titanium or nickel, or made of a conductive carbon material, or is a polymer-based current collector.

[0031] 16. The production / use of an anode according to embodiment 14 or embodiment 15, wherein the current collector is coated with a primer, such as a carbonaceous coating.

[0032] 17. Production of an anode / use according to any one of embodiments 14 to 16, wherein the current collector is a metal foil made of stainless steel or aluminum, preferably a current collector comprising carbon-coated aluminum foil.

[0033] 18. The production anode / use according to any one of embodiments 9 to 11, wherein the production anode / use is intended to pre-lithiate an electrode material, preferably to pre-lithiate an anode material, more preferably to pre-lithiate graphite, silicon, silicon oxide (SiO x ), pre-lithiation of silicon-carbon composite materials, carbon nanotubes or their mixtures.

[0034] 19. The production anode / use according to any one of embodiments 9 to 18, wherein the production anode is in the form of a membrane.

[0035] 20. A production electrolytic cell for producing lithium metal or its alloys or for pre-lithiating electrode materials, the production electrolytic cell comprising:

[0036] Used as relithiated lithium intercalation material to produce anodes,

[0037] Used as a current collector or said electrode material to produce a cathode, and

[0038] A generation electrolyte is disposed between the generation cathode and the generation anode, wherein the generation electrolyte comprises a generation lithium salt dissolved in a generation solvent.

[0039] 21. Use of a production electrolytic cell for producing lithium metal or its alloys or for pre-lithiating an electrode material, wherein the production electrolytic cell comprises:

[0040] Used as relithiated lithium intercalation material to produce anodes,

[0041] Used as a current collector or said electrode material to produce a cathode, and

[0042] A generation electrolyte is disposed between the generation cathode and the generation anode, wherein the generation electrolyte comprises a generation lithium salt dissolved in a generation solvent.

[0043] 22. The production electrolytic cell / use according to embodiment 20 or embodiment 21, wherein the relithiated lithium intercalation material is as defined in any one of embodiments 1 to 8.

[0044] 23. The production electrolysis cell / use according to any one of embodiments 20 to 22, wherein the production anode is as defined in any one of embodiments 9 to 19.

[0045] 24. The production electrolytic cell / use according to any one of embodiments 20 to 23, wherein the production electrolytic cell / use is intended for producing the lithium metal or the alloy thereof, preferably intended for producing lithium metal, preferably wherein the lithium metal or the alloy thereof is in the form of a film, preferably wherein the lithium metal or the alloy thereof is produced by electrodeposition, and wherein the current collector is used as a production cathode.

[0046] 25. The production electrolysis cell / use according to embodiment 24, wherein the current collector used as the production cathode is in the form of a foil.

[0047] 26. The production electrolytic cell / use according to embodiment 24 or embodiment 25, wherein operating conditions, such as stirring and / or temperature control, are used to change the morphology of the produced lithium metal or the alloy thereof.

[0048] 27. The production electrolytic cell / use according to any one of embodiments 24 to 26, wherein the current collector used as the production cathode is made of copper, aluminum, protected aluminum, carbon, stainless steel, titanium, zinc or nickel, or one of their alloys, or is a metallized polymer based current collector or a mixture thereof.

[0049] 28. The production electrolytic cell / use according to any one of embodiments 24 to 27, wherein the current collector used as the production cathode is made of protected copper or aluminum.

[0050] 29. The production electrolysis cell / use according to any one of embodiments 24 to 28, wherein the current collector used as the production cathode is protected by a protective layer.

[0051] 30. The production electrolysis cell / use of any one of embodiments 24 to 28, wherein the current collector used as the production cathode is unprotected.

[0052] 31. The production electrolytic cell / use of any one of embodiments 24 to 30, wherein the surface of the current collector used as the production cathode is treated or modified to improve its lithiophilicity.

[0053] 32. The production electrolytic cell / use of any one of embodiments 24 to 31, wherein the surface of the current collector used as a production cathode is treated or modified to have a 3D structure to improve the electrochemical performance of the lithium layer in the battery or increase its reaction rate, for example, when used to prepare an organolithium compound.

[0054] 33. The production electrolytic cell / use according to any one of embodiments 24 to 32, wherein the production electrolytic cell / use is intended for producing the alloy; preferably, the alloy comprises about 80% w / w or more lithium, more preferably about 85% w / w or more lithium, even more preferably about 90% w / w or more lithium, even more preferably about 95% w / w or more lithium, based on the total weight of the alloy.

[0055] 34. The production electrolysis cell / use according to embodiment 33, wherein the production electrolyte further comprises an alloying salt, preferably a salt of one or more of the following elements: sodium, potassium, magnesium, calcium, a transition metal, aluminum, gallium or tin, preferably a salt of aluminum or magnesium.

[0056] 35. The production electrolytic cell / use according to embodiment 34, wherein the alloying salt is (fluorosulfonyl) (trifluoromethanesulfonyl) imide salt, 2-trifluoromethyl-4,5-dicyanoimidazole (TDI) salt, 4,5-dicyano-1,2,3-triazole (DCTA) salt, bis(pentafluoroethylsulfonyl) imide (BETI) salt, difluorophosphate (DFP), chloride salt, bromide salt, fluoride salt, hexafluoroarsenate (AsF6), fluoroalkyl phosphate salt , tetrakis(trifluoroacetoxy)borate, bis(1,2-benzenediol (2-)-O,O′)borate, difluoro(oxalato)borate, nitrate, trifluoroacetate, hexafluorophosphate, tetrafluoroborate, bis(oxalato)borate (BOB) salt, perchlorate, bis(trifluoromethanesulfonyl)imide (TFSI) salt, bis(fluorosulfonyl)imide (FSI) salt, trifluoromethanesulfonate, or a salt containing an anion having the formula: BF2O4R x - (R x =C 2-4 alkyl).

[0057] 36. The production electrolytic cell / use according to any one of embodiments 24 to 32, wherein the production electrolyte is free of alloying salts and is intended for the production of lithium metal.

[0058] 37. The production electrolytic cell / use according to any one of embodiments 20 to 23, wherein the production electrolytic cell / use is intended for pre-lithiation of an electrode material, preferably for pre-lithiation of an anode material, more preferably for pre-lithiation of graphite, silicon, silicon oxide or a mixture thereof, and wherein the electrode material is used as a production cathode.

[0059] 38. The production electrolytic cell / use of any one of embodiments 20 to 37, wherein the production lithium salt is lithium (fluorosulfonyl) (trifluoromethanesulfonyl) imide, lithium 2-trifluoromethyl-4,5-dicyanoimidazole (LiTDI), lithium 4,5-dicyano-1,2,3-triazole (LiDCTA), lithium bis(pentafluoroethylsulfonyl) imide (LiBETI), lithium difluorophosphate (LiDFP), lithium chloride (LiCl), lithium bromide (LiBr), lithium hexafluoroarsenate (LiAsF6 - ), lithium fluoroalkyl phosphates [such as LiPF3(CF2CF3)3], lithium tetrakis(trifluoroacetoxy)borate (LiB(OCOCF3)4), bis(1,2-benzenediol ion (2-)-O, O') lithium borate LiB(C6O2)2, lithium difluoro(oxalate ion) borate (LiBF2(C2O4)), having the formula BF2O4R x - (R x =C 2-4 alkyl), LiCF3COO, LiF, LiNO3, LiPF6, LiBF4, LiBOB, LiClO4, LiTFSi, CF3SO3Li, LiFSi, or any combination thereof, preferably LiCF3COO, LiF, LiNO3, LiPF6, LiBF4, LiBOB, LiClO4, LiTFSi, CF3SO3Li, LiFSi, or any combination thereof.

[0060] 39. The production electrolytic cell / use of embodiment 38, wherein the produced lithium salt is a combination of CF3SO3Li and LiFSi.

[0061] 40. The production electrolytic cell / use according to any one of embodiments 20 to 39, wherein the production electrolyte further comprises one or more additives, preferably one or more additives that change the morphology and / or properties of the lithium metal or its alloys, one or more additives that affect phase nucleation energy, one or more additives that affect the deposition potential of the lithium or its alloys, and / or one or more additives that affect the electrodeposition efficiency of lithium; more preferably, the additives are the following:

[0062] Cyclic unsaturated carbonates, such as vinylene carbonate (VC),

[0063] Halogenated cyclic carbonates, such as fluoroethylene carbonate (FEC),

[0064] nitrates,

[0065] A lithium polymerization agent comprising a saturated or unsaturated hydrocarbon chain, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), a lithium passivating compound, and / or

[0066] Basic salts of organic acids, such as lithium difluoro(oxalate)borate (LiDFOB) or lithium oxalate.

[0067] 41. The production electrolysis cell / use of any one of embodiments 20 to 40, wherein the production solvent is an organic carbonate, an organic ester, an organic ether, an ionic liquid, or any combination thereof.

[0068] 42. The production electrolysis cell / use of embodiment 41, wherein the production solvent is ethylene carbonate (EC), propylene carbonate (PC), fluoroethylene carbonate (FEC), gamma-butyrolactone (gBL), ethyl propionate, diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), dimethoxyethane (DME), fluoroether, tetrafluoroethyltetrafluoropropyl ether (TTE), tetraethylene glycol dimethyl ether (TEGDME), or any combination thereof.

[0069] 43. The production electrolysis cell / use of embodiment 42, wherein the production solvent is a combination of EC and DEC.

[0070] 44. The production electrolysis cell / use according to any one of embodiments 20 to 43, wherein the production electrolysis cell is free of a membrane separating the production anode from the production cathode.

[0071] 45. The production electrolysis cell / use according to embodiment 44, wherein the production electrolysis cell is in a roll-to-roll configuration.

[0072] 46. ​​The production cell / use according to embodiment 44 or embodiment 45, wherein the production cell further comprises one or more calendering devices, such as pairs of calendering rolls, at regular intervals.

[0073] 47. A method for producing lithium metal or its alloys or pre-lithiating an electrode material, the method comprising:

[0074] a) providing a relithiated lithium intercalation material, and

[0075] b) carrying out an electrolytic reaction for producing lithium in a production electrolytic cell, wherein the production electrolytic cell comprises:

[0076] as the relithiated lithium intercalation material producing the anode,

[0077] as a current collector or said electrode material for producing a cathode, and

[0078] a generation electrolyte disposed between the generation cathode and the generation anode, wherein the generation electrolyte comprises a generation lithium salt dissolved in a generation solvent,

[0079] thereby enabling the electrodeposition of lithium metal or its alloys on the current collector used to produce the cathode, or introducing lithium into the electrode material, thereby producing a pre-lithiated electrode, and

[0080] This enables the production of partially or completely delithiated lithium intercalation materials.

[0081] 48. The method of embodiment 47, wherein the relithiated lithium intercalation material is as defined in any one of embodiments 1 to 8.

[0082] 49. The method of embodiment 47 or embodiment 48, wherein the generating an anode is as defined in any one of embodiments 9 to 19.

[0083] 50. The method of any one of embodiments 47 to 49, wherein the production electrolytic cell is as defined in any one of embodiments 20 to 46.

[0084] 51. The method of any one of embodiments 47 to 50, wherein the electrolysis reaction for producing lithium is performed by adjusting the cell potential between the producing anode and the producing cathode or between the cathode and a reference electrode.

[0085] 52. The method of any one of embodiments 47 to 50, wherein the electrolysis reaction to produce lithium is performed by adjusting the cell current.

[0086] 53. The method of embodiment 52, wherein the electrolysis reaction for producing lithium is carried out in a direct mode, a pulse mode, whether a simple (unidirectional) mode or a reverse mode, in a current-controlled mode.

[0087] 54. The method of embodiment 52 or embodiment 53, wherein the electrolysis reaction for producing lithium is performed at a fixed frequency or a variable frequency in a regulated current mode.

[0088] 55. The method of any one of embodiments 47 to 54, wherein step a) is performed in a roll-to-roll configuration.

[0089] 56. The method of any one of embodiments 47 to 55, wherein step b) is performed in a roll-to-roll configuration.

[0090] 57. The method according to any one of embodiments 47 to 56, wherein the partially or fully delithiated lithium intercalation material is lithium phosphate or partially or fully delithiated lithium oxide, preferably partially or fully delithiated Li w FePO4、Li w Mn2O4、Li 4+z Ti5O 12 or NMC(Li w Ni 1-x-y Mn x Co y MzO2).

[0091] 58. The method of embodiment 57, wherein the partially or fully delithiated lithium intercalation material is a partially or fully delithiated Li w FePO4.

[0092] 59. The method of any one of embodiments 47 to 58, wherein the relithiated lithium intercalation material is washed, preferably washed and dried, prior to use in step b).

[0093] 60. The method of any one of embodiments 47 to 59, wherein step a) comprises:

[0094] a′) providing a partially or fully delithiated lithium intercalation material, and

[0095] a″) relithiating the partially or fully delithiated lithium intercalation material, thereby enabling the production of a relithiated lithium intercalation material.

[0096] 61. The method according to embodiment 60, further comprising step c) of repeating steps a) and b) one or more times, using the partially or fully delithiated lithium intercalation material produced in step b) in steps a') and a").

[0097] 62. The method of embodiment 60 or embodiment 61, wherein the partially or fully delithiated lithium intercalation material supplied in step a') is the partially or fully delithiated lithium intercalation material produced in step b).

[0098] 63. The method of any one of embodiments 47 to 60, wherein the partially or fully delithiated lithium intercalation material is obtained from recycled used batteries.

[0099] 64. The method of any one of embodiments 47 to 63, wherein step a″) comprises performing the electrolytic relithiation reaction in an electrolytic relithiation cell, wherein the electrolytic relithiation cell comprises:

[0100] as said partially or fully delithiated intercalation material for a relithiated cathode,

[0101] Relithiated anode, and

[0102] a relithiated electrolyte disposed between the relithiated cathode and the relithiated anode, wherein the relithiated electrolyte comprises a relithiated lithium salt dissolved in a relithiated solvent,

[0103] This enables the partially or fully delithiated intercalation material to be relithiated and produces the relithiated lithium intercalation material.

[0104] 65. The method of embodiment 64, wherein the relithiation solvent is water.

[0105] 66. The method of embodiment 64 or embodiment 65, wherein the relithiation anode is made of a material that is compatible with the anode reaction occurring at the relithiation anode, preferably compatible with the oxygen evolution reaction.

[0106] 67. The method of any one of embodiments 64 to 66, wherein the relithiated anode is made of lead, platinum, titanium, another inert metal, or one of their alloys, or graphite.

[0107] 68. The method of any one of embodiments 64 to 67, wherein the relithiated anode is a dimensionally stable anode.

[0108] 69. A method according to any one of embodiments 64 to 68, wherein the relithiation electrolyte further comprises one or more additives; preferably one or more additives that improve the conductive properties of the relithiation electrolyte; more preferably comprises a salt of an alkali cation other than lithium or an alkaline earth cation (preferably potassium or magnesium) and an anion compatible with the electrolytic relithiation reaction (preferably sulfate or bicarbonate).

[0109] 70. The method of any one of embodiments 64 to 69, wherein the relithiation salt is Li2CO3, LiHCO3, LiOH, LiNO3, LiOH, Li2SO4, LiCH3COO, LiFSI, LiTFSI or Li2C2O4 or a mixture thereof, preferably the relithiation salt is LiHCO3, Li2SO4 or a mixture thereof, preferably the relithiation salt is Li2SO4.

[0110] 71. The method of any one of embodiments 64 to 70, wherein the relithiation salt is an inexpensive lithium salt.

[0111] 72. The method of any one of embodiments 64 to 71, wherein the relithiation solvent is water and the relithiation salt is a water-soluble relithiation salt.

[0112] 73. The method of any one of embodiments 64 to 72, wherein the relithiation salt is a water-soluble relithiation salt having a water solubility greater than that of LiHCO 3 .

[0113] 74. The method of embodiment 73, wherein the water-soluble relithiation salt having a water solubility greater than that of LiHCO 3 is LiNO 3 , Li 2 SO 4 , or LiCH 3 COO.

[0114] 75. The method of any one of embodiments 64 to 74, further comprising the step of generating the relithiation salt in the electrolytic relithiation cell.

[0115] 76. The method of embodiment 75, comprising adding a lithium precursor and a reagent to the electrolytic relithiation cell, and reacting the lithium precursor with the reagent to form the relithiation salt.

[0116] 77. A method according to embodiment 76, wherein the lithium precursor and the reagent are added to a salt formation compartment of the electrolytic relithiation cell, and the salt formation compartment is connected to the fluid of the main compartment of the electrolytic relithiation cell; the main compartment contains the relithiation cathode and the relithiation anode.

[0117] 78. The method of any one of embodiments 64 to 74, wherein the relithiation salt is prepared prior to addition to the electrolytic relithiation cell.

[0118] 79. The method of embodiment 78, further comprising reacting a lithium precursor and a reagent in a reactor separate from the electrolytic relithiation cell to obtain the relithiation salt, and then adding the relithiation salt to the electrolytic relithiation cell.

[0119] 80. The method according to any one of embodiments 76, 77 and 79, wherein the lithium precursor is Li2CO3, LiOH or a mixture thereof, preferably Li2CO3.

[0120] 81. The method of any one of embodiments 76, 77, 79 or 80, wherein the reagent is CO2, H2SO4, nitric acid, acetic acid, oxalic acid or an acid form of a sulfonyl imide salt or a mixture thereof, preferably CO2 or H2SO4 or a mixture thereof.

[0121] 82. The method of embodiment 81, wherein the reagent is CO2.

[0122] 83. The method of embodiment 81, wherein the reagent is H2SO4.

[0123] 84. The method of any one of embodiments 64 to 83, wherein the electrolytic relithiation reaction is performed by adjusting the cell potential between the relithiated anode and the relithiated cathode or between the relithiated cathode and a reference electrode.

[0124] 85. The method of any one of embodiments 64 to 83, wherein the electrolytic relithiation reaction is performed by adjusting the cell current.

[0125] 86. The method of embodiment 85, wherein the electrolysis reaction can be performed in a direct mode, a pulse mode, whether a simple (unidirectional) mode or a reverse mode, in a current-controlled mode.

[0126] 87. The method of embodiment 85 or embodiment 86, wherein the electrolysis reaction can be performed at a fixed frequency or a variable frequency in a current-controlled mode.

[0127] 88. The method of any one of embodiments 47 to 63, wherein step a″) comprises (i) adding the partially or fully delithiated intercalation material to a solution containing a reducing agent and a relithiating salt in a solvent; thereby enabling relithiation of the partially or fully delithiated intercalation material and producing the relithiated lithium intercalation material.

[0128] 89. The method of embodiment 88, further comprising (ii) separating the relithiated lithium intercalation material from the solution; and (iii) electrochemically treating the solution separated in step (ii) to regenerate the reducing agent.

[0129] 90. The method of embodiment 88 or embodiment 89, wherein the relithiation salt is as described in any one of embodiments 70 to 74.

[0130] 91. The method of any one of embodiments 88 to 90, wherein the reducing agent is the reducing member of a redox pair, the reducing member having a redox potential lower than the redox potential of the partially or fully delithiated intercalation material.

[0131] 92. The method of embodiment 91, wherein the redox couple comprises an Fe(III) / Fe(II) complex.

[0132] 93. The method of embodiment 92, wherein the redox couple is [Fe(CN)6] 3- / Fe(CN)6] 4- 、[Fe(nta)] / [Fe(nta)] - 、[Fe(tdpa)] 2 - / Fe(tdpa)] 3-, [Fe(edta)] - / [Fe(edta)] 2- , [Fe(citrate)] / [Fe(citrate)] - , [Fe(III)-TEA] / [Fe(II)-TEA] or [Fe(oxalate)] + / [Fe(oxalate)].

[0133] 94. The method of any one of embodiments 88 to 93, wherein step (i) further comprises deoxygenating the solution.

[0134] 95. The method of any one of embodiments 88 to 94, wherein steps (i) and / or (iii) are performed in the absence of oxygen.

[0135] 96. The method of any one of embodiments 88-95, further comprising adjusting the pH of the solution.

[0136] 97. The method of any one of embodiments 88 to 96, wherein the solvent is an aqueous solvent.

[0137] 98. The method of any one of embodiments 88 to 97, wherein step (iii) is performed in an electrolytic cell by passing power between at least one cathode and at least one anode.

[0138] 99. The method of embodiment 98, wherein the electrolytic cell comprises at least one ionic or non-ionic membrane installed between the anode and the cathode to protect the regenerated reducing agent.

[0139] 100. The method of embodiment 98 or embodiment 99, wherein the electrolytic cell further comprises a system for maintaining a deoxygenated solution.

[0140] 101. The method of any one of embodiments 98 to 100, wherein step (iii) is performed by adjusting the cell potential between the anode and the cathode or between the cathode and a reference electrode.

[0141] 102. The method of any one of embodiments 98 to 100, wherein step (iii) is performed by adjusting the cell current.

[0142] 103. The method of embodiment 102, wherein the relithiation reaction is performed in a direct mode, a pulse mode, whether a simple (unidirectional) mode or a reverse mode, under a regulated current mode.

[0143] 104. The method of embodiment 102 or embodiment 103, wherein the relithiation reaction is performed at a fixed frequency or a variable frequency in a regulated current mode.

[0144] 105. The method according to any one of embodiments 47 to 104, further comprising washing and drying the current collector with the lithium metal or the alloy thereof, or the pre-lithiated electrode produced in step b).

[0145] 106. A method according to any one of embodiments 47 to 105, which further comprises using the collector having the lithium metal or the alloy thereof, or the pre-lithiated electrode as a negative electrode in a primary or secondary lithium battery, preferably a lithium-ion battery or an all-solid-state battery, as a source of lithium metal or the alloy thereof for pre-lithiating electrode materials, or as a source of lithium metal or the alloy thereof for manufacturing an energy storage system.

[0146] 107. The method of any one of embodiments 47 to 106, further comprising rolling the current collector having the lithium metal or the alloy thereof to change the morphology, density, or film thickness of the lithium metal or the alloy thereof.

[0147] 108. The method of any one of embodiments 47 to 107, further comprising processing the current collector having the lithium metal or the alloy thereof to have a 3D structure.

[0148] 109. The method of any one of embodiments 47 to 108, further comprising treating the current collector having the lithium metal or the alloy thereof to improve its electrochemical performance in a battery.

[0149] 110. The method of any one of embodiments 47 to 105, further comprising using the current collector having the lithium metal or the alloy thereof as a lithium source to produce an organolithium compound.

[0150] 111. The method of embodiment 110, wherein the lithium metal or the alloy thereof is reacted with a reagent such as an alkyl halide to produce the organolithium compound.

[0151] 112. The method according to embodiment 111, further comprising transferring the current collector having the lithium metal or the alloy thereof produced in step b) to a separate reactor, preferably in roll-to-roll mode, and reacting the lithium metal or the alloy thereof with a reactant in the separate reactor to produce the organic lithium compound.

[0152] 113. The method according to any one of embodiments 47 to 112, which is intended to pre-lithiate an electrode material, preferably to pre-lithiate an anode material, more preferably to pre-lithiate graphite, silicon, silicon oxide (SiO x ), silicon-carbon composite materials, carbon nanotubes or mixtures thereof are pre-lithiated, and wherein the electrode material is used to produce a cathode.

[0153] 114. A method according to any one of embodiments 47 to 112, which is intended to produce the lithium metal or the alloy thereof, preferably intended to produce the lithium metal, preferably wherein the lithium metal or the alloy thereof is produced by electrodeposition, and wherein the current collector is used to produce the cathode.

[0154] 115. The method according to embodiment 114, wherein the lithium metal or the alloy thereof is electrolytically deposited on the current collector in the form of a film, preferably a high-purity film.

[0155] 116. A lithium electrode comprising a current collector comprising lithium metal or an alloy thereof as produced by the method of any one of embodiments 47 to 115.

[0156] 117. A lithium battery comprising the lithium electrode according to embodiment 116, preferably wherein the battery is a lithium ion battery or an all-solid-state battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0157] In the attached figure:

[0158] Figure 1 A schematic diagram showing an example of the process according to the invention using LiHCO 3 as the relithiation salt is shown.

[0159] Figure 2 A schematic diagram showing an embodiment of the method according to the invention using Li 2 SO 4 as the relithiation salt is shown.

[0160] Figure 3 A bifacial production electrolysis cell with a multi-stage electrolysis configuration is shown.

[0161] Figure 4 Shown is the cell potential versus time (upper black line) for the galvanostatic electrodeposition of lithium metal described in Example 4. The lower grey line represents the applied current density.

[0162] Figure 5 Shown is the cell potential versus time (upper black line) for galvanostatic electrodeposition of lithium metal in the button cells of Example 5. The lower grey line represents the applied current density.

[0163] Figure 6A chronocoulometry method is shown for the relithiation process of delithiated LiFePO4 (FP) in relithiated LiFePO4 (LFP). Note that delithiated LiFePO4 is sometimes referred to herein as FePO4 (although it may contain residual lithium) or FP.

[0164] Figure 7 Shown is a comparison of the X-ray diffraction spectra of the pristine LFP electrode, the FP electrode before relithiation, and the LFP electrode after relithiation.

[0165] Figure 8 Shown is a comparison of cycling stability between cells (triangles) using commercially available lithium prepared by physical vapor deposition (PVD) as anode and cells (in duplicate) using electrolytically deposited lithium (LiED) (obtained from Example 4) as anode (squares and diamonds).

[0166] Figure 9 The cell potential for galvanostatic electrodeposition of lithium metal is shown as a function of time (upper black line). The lower grey line represents the applied current density.

[0167] Figure 10A The appearance of the electrodeposited lithium of Example 7 before rolling is shown.

[0168] Figure 10B The appearance of the electrodeposited lithium of Example 7 after calendaring is shown.

[0169] Figure 11 Shown is a scanning electron microscope (SEM) micrograph of a cross section of the electrodeposited and rolled lithium of Example 7. The thicker top layer corresponding to the electrodeposited lithium is 7.52 μm thick, while the thinner bottom layer corresponding to the copper foil is 3.37 μm thick.

[0170] Figure 12 The cycling stability of the electrodeposited lithium from Example 7 was compared with that of lithium foil prepared by PVD.

[0171] Figure 13 The cycling stabilities of lithium electrodeposited on different current collectors were compared.

[0172] Figure 14 The cell potential for the galvanostatic electrodeposition of lithium metal in Example 8.1 is shown as a function of time (upper black line). The lower grey line represents the applied current density.

[0173] Figure 15 The cell potential for the galvanostatic electrodeposition of lithium metal in Example 8.2 is shown as a function of time (upper black line). The lower grey line represents the applied current density.

[0174] Figure 16The cell potential for the galvanostatic electrodeposition of lithium metal in Example 8.3 is shown as a function of time (upper black line). The lower grey line represents the applied current density.

[0175] Figure 17 Shown is the cell potential versus time (upper black line) for galvanostatic electrodeposition of lithium metal in Example 9. The lower grey line represents the applied current density.

[0176] Figure 18 The appearance of the electrodeposited lithium of Example 9 is shown.

[0177] Figure 19 The cell potential is shown as a function of time (upper black line) for the galvanostatic relithiation of LFP delithiated to form LFP in Example 10. The lower grey line represents the applied current density.

[0178] Figure 20 FTIR spectra of the delithiated (FP) and relithiated (LFP) electrodes of Example 10 are shown.

[0179] Figure 21 Shown are the cell potentials as a function of electrodeposition time (lithium ED) for Example 10 (lithium ED from relithiated LFP, solid line) and Example 8.2 (lithium ED from pristine LFP, dashed line).

[0180] Figure 22 The evolution of the potential of the LTO working electrode during relithiation of Example 11 is shown.

[0181] Figure 23 The anodic current linear sweep voltammetry curve of the relithiated LTO electrode of Example 11 is shown.

[0182] Figure 24 The effects of various additives added to the electrolyte during the electrodeposition of lithium were compared.

[0183] Figure 25 A titration curve prepared to determine the concentration of n-butyllithium in n-hexane is shown (Example 13).

[0184] Figure 26 Shown is the galvanostatic prelithiation of a graphite anode with an LFP counter electrode as the lithium source.

[0185] Figure 27 Galvanostatic prelithiation of a SiOx anode with an LFP counter electrode as the lithium source is shown.

[0186] Figure 28 The potential curves of fresh graphite anode and pre-lithiated anode are compared as a function of charge in the first formation cycle.

[0187] Figure 29The potential curves of fresh SiOx anode and pre-lithiated anode are compared as a function of charge in the first formation cycle. DETAILED DESCRIPTION

[0188] Turning now to the present invention in more detail, the present invention relates to a relithiated lithium intercalation material for producing lithium metal or its alloys or for prelithiating an electrode material. In a related aspect, the present invention relates to the use of a relithiated lithium intercalation material for producing lithium metal or its alloys or for prelithiating an electrode material.

[0189] In certain embodiments of the present invention, the materials / uses are used to produce lithium metal or its alloys. In certain embodiments, lithium metal is produced. In other embodiments, an alloy is produced. In preferred embodiments, the lithium metal or its alloy is in the form of a film. Preferably, the lithium metal or its alloy is produced by electrodeposition.

[0190] In certain embodiments of the present invention, the material / use is for pre-lithiation of an electrode material. The electrode material may be any electrode material that may experience loss of active lithium during the first operating cycle of the battery. In certain embodiments, the electrode material is graphite, silicon, silicon oxide (SiO x ), silicon-carbon composite materials, carbon nanotubes or mixtures thereof.

[0191] Here, "lithium intercalation material" is a material that reversibly contains lithium ions (Li + ) materials. Such materials are commonly used, for example, in the manufacture of cathodes for Li-ion batteries. + The insertion of ions into such materials is referred to herein as "lithiation" of the material. + The deintercalation of ions in such materials is referred to herein as "delithiation." Delithiation can be partial or complete. Complete delithiation means that all of the Li+ ions that could be deintercalated have done so under any particular set of conditions that may be applied. Partial delithiation means that only some of these ions have been deintercalated.

[0192] Herein, "relithiation" refers only to the lithiation of a lithium intercalation material after it has been partially or fully delithiated. Thus, a "relithiated lithium intercalation material" is a partially or fully delithiated lithium intercalation material that has been relithiated.

[0193] Examples of partially or fully delithiated lithium intercalation materials are lithium intercalation materials that have degraded due to the loss of lithium. Such materials are produced by the method of the present invention and can be relithiated and reused in the method of the present invention. For example, such delithiated lithium intercalation materials are also found in the spent cathodes of used Li-ion batteries, which can cause a decrease in capacity. When the partially or fully delithiated lithium intercalation material is relithiated, it recovers at least some of its lithium ions and thus restores some of its electrochemical properties. Preferably, the relithiated lithium intercalation material has recovered at least 50%, preferably at least 75%, more preferably at least 85%, even more preferably at least 95% and even more preferably at least 99% of the previously deintercalated lithium ions.

[0194] There is no particular limitation on the relithiated lithium intercalation material.

[0195] In a preferred embodiment, the relithiated lithium intercalation material is lithium phosphate or lithium oxide. In a preferred embodiment, the relithiated lithium intercalation material is one of the following:

[0196] ·Li w FePO4 (where w ≤ 1.1, preferably w is 1),

[0197] ·Li w Fe 1-x Mn x PO4 (where w ≤ 1.1, preferably w is 1; 0 < x ≤ 1, preferably 0.2 < x ≤ 0.4),

[0198] ·Li w Mn2O4 (where w ≤ 1.1, preferably w is 1),

[0199] ·Li w Mn 1.5 Ni 0.5 O4 (where w ≤ 1.1, preferably w is 1),

[0200] ·Li 4+z Ti5O 12 (where 0 < z ≤ 3), or

[0201] ·NMC (Li w Ni 1-x-y Mn x Co y O2, where w ≤ 1.3, preferably w is 1; 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, and 0 ≤ z ≤ 1, and M is aluminum, magnesium, titanium, niobium, zirconium, tungsten, molybdenum, yttrium, lanthanum, tantalum or a mixture thereof).

[0202] Note that the lithium intercalation material may contain excess lithium, which means that its lithium content is higher than the stoichiometric ratio.

[0203] In a preferred embodiment, the relithiated lithium intercalation material is Li w FePO4.

[0204] In preferred embodiments, the relithiated lithium intercalation material has been prepared from a partially or fully delithiated lithium intercalation material produced by the method of the present invention. In other embodiments, the relithiated lithium intercalation material is derived from spent electrodes, such as those recovered from batteries, and then relithiated.

[0205] Producing anode

[0206] The present invention similarly relates to a production anode for producing lithium metal or its alloys or for pre-lithiating an electrode material, the anode comprising a relithiated lithium intercalation material. This anode is referred to as a "production anode" to distinguish it from another anode used for an electrolytic relithiation reaction (which will be referred to as a "relithiated anode") hereinafter. In a related aspect, the present invention relates to the use of a relithiated lithium intercalation material as an anode for producing lithium metal or its alloys or for pre-lithiating an electrode material.

[0207] In certain embodiments, the anode is designed to produce lithium metal or its alloys. In certain embodiments, lithium metal is produced. In certain embodiments, a lithium alloy is produced. Preferably, the lithium metal or its alloy is in the form of a film. Preferably, the lithium metal or its alloy is produced by electrodeposition.

[0208] In certain embodiments, the anode is intended to pre-lithiate the electrode material. The electrode material is as defined above.

[0209] The relithiated lithium intercalation material is as defined above.

[0210] In certain embodiments, the anode is produced to perform an electrolysis reaction for producing lithium.

[0211] In certain embodiments, the production anode further comprises a current collector, and the relithiated lithium intercalation material is deposited on the current collector. This current collector can be made of any conductive material, including any material used for battery current collectors. In certain embodiments, this current collector is a metal foil, preferably made of copper, aluminum, stainless steel, titanium or nickel, or made of a conductive carbon material, or is a polymer-based current collector. In a most preferred embodiment, this current collector is covered with a primer to improve the adhesion of the lithium intercalation material (such as a carbonaceous coating). In a preferred embodiment, this current collector is a metal foil made of stainless steel or aluminum, preferably a current collector comprising carbon-coated aluminum foil.

[0212] In a preferred embodiment, the anode is produced in the form of a membrane.

[0213] Producing electrolytic cells

[0214] The present invention similarly relates to a production electrolytic cell for producing lithium metal or its alloys or for pre-lithiating electrode materials, comprising:

[0215] Used as relithiated lithium intercalation material to produce anodes,

[0216] a current collector for producing a cathode, and

[0217] A generation electrolyte is located between the generation cathode and the generation anode, wherein the generation electrolyte comprises a generation lithium salt dissolved in a generation solvent.

[0218] Here, these cells, cathodes, electrolytes, salts and solvents are respectively referred to as "generation cells", "generation cathodes", etc., to distinguish them from the cells, cathodes, electrolytes, salts and solvents used for the electrolytic relithiation reaction described below and respectively referred to as "relithiation cells", "relithiation cathodes", etc.

[0219] In a related aspect, the present invention relates to the use of such electrolytic cells for producing lithium metal or its alloys or for pre-lithiating electrode materials.

[0220] The relithiated lithium intercalation material is as defined above.

[0221] The anode is generated as defined above.

[0222] The resulting lithium salt can be any salt that is compatible with lithium metal (or the resulting alloy). In certain embodiments, the generated lithium salt is lithium (fluorosulfonyl) (trifluoromethanesulfonyl) imide, lithium 2-trifluoromethyl-4,5-dicyanoimidazole (LiTDI), lithium 4,5-dicyano-1,2,3-triazole (LiDCTA), lithium bis(pentafluoroethylsulfonyl) imide (LiBETI), lithium difluorophosphate (LiDFP), lithium chloride (LiCl), lithium bromide (LiBr), lithium hexafluoroarsenate (LiAsF6-), lithium fluoroalkyl phosphates [such as LiPF3(CF2CF3)3], lithium tetrakis(trifluoroacetoxy)borate (LiB(OCOCF3)4), lithium bis(1,2-benzenediolate (2-)-O,O')borate LiB(C6O2)2, lithium difluoro(oxalate)borate (LiBF2(C2O4)), lithium fluoride having the formula BF2O4R x - (R x =C 2-4alkyl), LiCF3COO, LiF, LiNO3, LiPF6, LiBF4, LiBOB, LiClO4, LiTFSi, CF3SO3Li, LiFSi or any combination thereof, preferably LiCF3COO, LiF, LiNO3, LiPF6, LiBF4, LiBOB, LiClO4, LiTFSi, CF3SO3Li, LiFSi or any combination thereof. In a preferred embodiment, the generated lithium salt is a combination of CF3SO3Li and LiFSi.

[0223] In certain embodiments, the electrolyte further comprises one or more additives. Non-limiting examples of additives include additives that change the morphology and / or properties of the lithium metal or its alloys, additives that affect the phase nucleation energy, additives that affect the deposition potential of the lithium metal or its alloys, and additives that affect the electrodeposition efficiency of the lithium metal or its alloys. In certain embodiments, the additives are the following:

[0224] Cyclic unsaturated carbonates, such as vinylene carbonate (VC),

[0225] Halogenated cyclic carbonates, such as fluoroethylene carbonate (FEC),

[0226] Nitrates,

[0227] lithium polymerizing agents containing saturated or unsaturated hydrocarbon chains, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),

[0228] Lithium passivating compounds, and / or

[0229] • Basic salts of organic acids, such as lithium difluoro(oxalate)borate (LiDFOB) or lithium oxalate.

[0230] The generation solvent can be any solvent commonly used in Li-ion batteries. In certain embodiments, the generation solvent is an organic carbonate, an organic ester, an organic ether, an ionic liquid, or any combination thereof. In a preferred embodiment, the generation solvent is ethylene carbonate (EC), propylene carbonate (PC), fluoroethylene carbonate (FEC), γ-butyrolactone (gBL), ethyl propionate, diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), dimethoxyethane (DME), fluoroether, tetrafluoroethyl tetrafluoropropyl ether (TTE), tetraethylene glycol dimethyl ether (TEGDME), or any combination thereof.

[0231] In certain embodiments, the production electrolysis cell lacks a membrane separating the production anode from the production cathode.

[0232] In certain embodiments, the electrolytic cell is produced in a roll-to-roll configuration. In fact, the configuration of the cell without a membrane allows the use of a multi-stage roll-to-roll configuration, such as Figure 3 In such embodiments, the cell may further comprise one or more calendering devices, such as pairs of calendering rollers, for example at regular intervals, to densify the electrodeposited lithium (or lithium alloy) film during its formation.

[0233] In certain embodiments, the production electrolytic cell is intended to pre-lithiate an electrode material. The electrode material is as defined above and serves as a production cathode. In use, the production electrolytic cell is capable of introducing lithium into the electrode material.

[0234] In other embodiments, the production electrolytic cell is intended to produce lithium metal or its alloys. The current collector serves as the production cathode. In certain embodiments, lithium metal is produced. In certain embodiments, a lithium alloy is produced. Preferably, the lithium metal or its alloy is in the form of a film. Preferably, the lithium metal or its alloy is produced by electrodeposition. In use, the production electrolytic cell enables electrodeposition of a film of lithium metal or its alloy onto the current collector serving as the production cathode.

[0235] In a preferred embodiment, operating conditions such as agitation and / or temperature control are used to modify the morphology of the produced lithium metal or its alloys.

[0236] In a preferred embodiment, the current collector used to create the cathode is in the form of a foil.

[0237] The current collector used to generate the cathode can be made of any conductive material, including any material used as a current collector for batteries. In certain embodiments, the current collector is made of copper, aluminum, protected aluminum, carbon, stainless steel, titanium, zinc or nickel, or one of their alloys, or is based on a metallized polymer, or a combination thereof.

[0238] In a preferred embodiment, the current collector is made of protected copper or aluminum.

[0239] The current collector used to generate the cathode may or may not be protected by a protective layer. The surface of the current collector may be treated or modified to improve its lithium affinity. The surface of the current collector may be treated or modified to have a 3D structure to improve the electrochemical performance of the lithium metal (or alloy) layer in the battery or increase its reaction rate, for example, when used to produce an organolithium compound.

[0240] In certain embodiments, the production electrolyte further comprises one or more alloying salts. An alloying salt is a salt of one or more metals that can form an alloy with lithium. When an alloying salt is used, a lithium alloy will be produced at the cathode. In alternative embodiments, the production electrolyte does not contain an alloying salt, and thus lithium metal (rather than a lithium alloy) will be produced at the cathode.

[0241] In a preferred embodiment, the alloy comprises primarily lithium. In a preferred embodiment, the alloy comprises about 80% w / w or more lithium, preferably about 85% w / w or more lithium, more preferably about 90% w / w or more lithium, even more preferably about 95% w / w or more lithium, based on the total weight of the alloy.

[0242] In certain embodiments, the alloying salt is a salt of one or more of the following elements: sodium, potassium, magnesium, calcium, a transition metal, aluminum, gallium, or tin; preferably aluminum or magnesium.

[0243] In certain embodiments, the alloying salt is (fluorosulfonyl) (trifluoromethanesulfonyl) imide salt, 2-trifluoromethyl-4,5-dicyanoimidazole (TDI) salt, 4,5-dicyano-1,2,3-triazole (DCTA) salt, bis(pentafluoroethylsulfonyl) imide (BETI) salt, difluorophosphate (DFP), chloride salt, bromide salt, fluoride salt, hexafluoroarsenate (AsF6), fluoroalkyl phosphate, tetrakis(trifluoroacetyloxy) oxalato)borate, bis(1,2-benzenediolate (2-)-O,O')borate, difluoro(oxalato)borate, nitrate, trifluoroacetate, hexafluorophosphate, tetrafluoroborate, bis(oxalato)borate (BOB) salt, perchlorate, bis(trifluoromethanesulfonyl)imide (TFSI) salt, bis(fluorosulfonyl)imide (FSI) salt, trifluoromethanesulfonate, or a salt containing an anion having the formula: BF2O4R x - (R x =C 2-4 alkyl).

[0244] Method for producing lithium metal / alloys thereof or for pre-lithiating electrode materials

[0245] The present invention similarly relates to a method for producing lithium metal or its alloys or for pre-lithiating an electrode material, the method comprising:

[0246] a) providing a relithiated lithium intercalation material, and

[0247] b) carrying out an electrolytic reaction for producing lithium in a production electrolytic cell, the production electrolytic cell comprising:

[0248] The relithiated lithium intercalation material as a producing anode

[0249] as a current collector or said electrode material for producing a cathode, and

[0250] a generation electrolyte disposed between the generation cathode and the generation anode, the generation electrolyte comprising a generation lithium salt dissolved in a generation solvent,

[0251] thereby enabling the electrodeposition of lithium metal or its alloy on said current collector serving as a cathode, or introducing lithium into said electrode material serving as a cathode, thereby producing a pre-lithiated electrode, and

[0252] This enables the production of partially or completely delithiated lithium intercalation materials.

[0253] In certain embodiments, the methods are used to produce lithium metal or its alloys. In certain embodiments, lithium metal is produced. In other embodiments, lithium alloys are produced. In all of these embodiments, a current collector is used to produce a cathode. Preferably, the lithium metal or its alloy is in the form of a film.

[0254] In other embodiments, the method is used to pre-lithiate an electrode material. The electrode material is as defined above and is used to generate a cathode.

[0255] This approach, as well as the materials, anodes, and cells (and their uses) described in the previous sections, has several advantages.

[0256] It avoids the use of any membranes in the production cell, which reduces costs, avoids contamination issues (particularly water leaks) that could affect the purity of the lithium, and avoids downtime due to membrane maintenance. This makes it possible to use a multi-stage roll-to-roll configuration with optional calendaring inside the production cell, which greatly reduces the space required for the process and doubles the production speed.

[0257] • This allows the use of cathode materials previously used in secondary batteries (to make relithiated lithium intercalation materials) and enables recycling of used secondary batteries.

[0258] • The method can be closed-loop, thereby limiting environmental impact and ensuring safety.

[0259] • The method enables the production of ultrathin, uniform lithium metal electrodes with high purity at low cost without the need for additional purification steps.

[0260] • The method produces lithium films or foils without melting the lithium.

[0261] • The method does not require high temperature electrolysis.

[0262] The lithium produced can be used to make primary and secondary lithium-based batteries, as well as to make organolithium compounds and pre-lithiate electrode materials.

[0263] On relithiation, the anode reaction releases oxygen, rather than chlorine (which is non-corrosive and easy to handle).

[0264] • The lithium salt used can be a cheap, easily purified lithium salt such as lithium carbonate, or even low purity lithium carbonate or any other lithium salt.

[0265] In a preferred embodiment, the relithiated lithium intercalation material of the method of the present invention is as defined in the preceding section.

[0266] In a preferred embodiment, the anode produced by the method of the present invention is as defined in the preceding section.

[0267] In a preferred embodiment, the production electrolytic cell of the method of the present invention is as defined in the preceding section.

[0268] Preferably, the current collector or pre-lithiated electrode having lithium metal or its alloy is washed, for example with an organic solvent, and dried before use. Therefore, in one embodiment, the method further comprises washing and drying the current collector or pre-lithiated electrode having lithium metal or its alloy produced in step b).

[0269] Step b)

[0270] In step b), the relithiated lithium intercalation material acts as an anode to provide lithium ions for the electrodeposition of lithium metal or its alloys or for the prelithiation of cathode materials. + .

[0271] Lithium metal or its alloys are deposited on a current collector that acts as the cathode. Lithium metal or its alloys are typically electrolytically deposited on the current collector in the form of a thin, generally high-purity film. Alternatively, lithium is introduced into the electrode material used as the cathode.

[0272] The electrochemical reactions at the cathode and anode in the electrolysis cell are as follows:

[0273] Cathode reaction: Li + +e - →Li

[0274] Anodic reaction (when LiFePO4 is used as the relithiation lithium intercalation material):

[0275] LiFePO4→FePO4+e - +Li +

[0276] A partially or fully delithiated lithium intercalation material (FePO 4 in the above example) is produced at the anode and can be used as starting material in step a) to provide a relithiated lithium intercalation material and thereby possibly reused in step b).

[0277] In certain embodiments, the electrolysis reaction for generating lithium is performed by adjusting the cell potential between the generating anode and the generating cathode or between the generating cathode and a reference electrode.

[0278] In certain embodiments, the electrolytic reaction for producing lithium is performed by regulating the cell current. In certain embodiments, under the regulated current mode, the electrolytic reaction for producing lithium can be performed in direct mode, pulse mode, whether the pulse mode is a simple (unidirectional) mode or a reverse mode. Similarly, under the regulated current mode, the electrolytic reaction for producing lithium can be performed at a fixed frequency or a variable frequency.

[0279] In certain embodiments, step b) is performed in a roll-to-roll configuration. In fact, the configuration of the membrane-free electrochemical generation cell used in step b) enables the use of a multi-stage roll-to-roll configuration, such as for example Figure 3 In such embodiments, the cell may further comprise one or more calendering devices, such as calendering rollers, for example at regular intervals, to densify the electrodeposited lithium film during its formation.

[0280] Step a)

[0281] As mentioned above, a relithiated lithium intercalation material is a partially or fully delithiated lithium intercalation material that has been relithiated.

[0282] The partially or completely delithiated lithium intercalation material is not particularly limited. It should be selected so that it is stable under the conditions used for relithiation (electrolyte, etc.). In a preferred embodiment, the partially or completely delithiated lithium intercalation material is lithium phosphate or partially or completely delithiated lithium oxide, preferably Li w FePO4、Li w Mn2O4、Li 4+z Ti5O 12 or partially or completely delithiated NMC (Li w Ni 1-x-y Mn x Co y M z In a preferred embodiment, the partially or completely delithiated lithium intercalation material is a partially or completely delithiated Li w FePO4 (preferably w is 1).

[0283] In certain embodiments, step a) is performed in a roll-to-roll configuration.

[0284] In certain embodiments, step a) may comprise:

[0285] a′) providing a partially or fully delithiated lithium intercalation material, and

[0286] a″) relithiating the partially or fully delithiated lithium intercalation material, thereby producing a relithiated lithium intercalation material

[0287] Subsequently, the relithiated lithium intercalation material is used in step b).

[0288] In a preferred embodiment, the relithiated lithium intercalation material is washed, preferably washed and dried, before use in step b).

[0289] In certain embodiments, the partially or fully delithiated lithium intercalation material is obtained from recycled used batteries.

[0290] As indicated above, in certain embodiments (preferably when the method of the present invention is repeated or continuous), the partially or fully delithiated lithium intercalation material of step a′) may be the material produced in step b). Thus, in certain embodiments, the method further comprises a step c) of repeating steps a) and b) one or more times, using the partially or fully delithiated lithium intercalation material produced in step b) in steps a′) and a″).

[0291] The partially or fully delithiated lithium intercalation material may be relithiated in step a″) by any method known in the art.

[0292] Relithiation by electrolysis using a lithium salt electrolyte

[0293] In a preferred embodiment, step a″) comprises performing an electrolytic relithiation reaction in an electrolytic relithiation cell comprising:

[0294] as said partially or fully delithiated intercalation material for a relithiated cathode,

[0295] Relithiated anode, and

[0296] a relithiated electrolyte, the relithiated electrolyte being located between the relithiated cathode and the relithiated anode,

[0297] The relithiation electrolyte comprises a relithiation lithium salt dissolved in a relithiation solvent,

[0298] This enables the partially or fully delithiated intercalation material to be relithiated and produces the relithiated lithium intercalation material.

[0299] In this electrolysis reaction, the relithiated lithium salt is used as the lithium ion + The source of lithium, and the partially or fully delithiated intercalation material is used as the cathode. The general reaction is as follows:

[0300] Anodic reaction (when FePO4 is used as lithium intercalation material for delithiation):

[0301] 2Li + +2e - +2FePO4→2LiFePO4

[0302] Anodic reaction (when LiHCO3 is used as the relithiation lithium salt):

[0303] 2HCO3 - -2e - →1 / 2O2+H2O+2CO2

[0304] The relithiation solvent can be any solvent or mixture thereof that can dissolve the lithium salt and support a compatible anode reaction. In a preferred embodiment, the relithiation solvent is water, which is an advantage of the present invention.

[0305] The anode material is not particularly limited. In certain embodiments, the relithiated anode is made of a material compatible with the anode reaction, preferably the oxygen evolution reaction. In preferred embodiments, the relithiated anode is made of lead, platinum, titanium, another inert metal, or an alloy thereof, or graphite. In preferred embodiments, the relithiated anode is a dimensionally stable anode.

[0306] In certain embodiments, the relithiation electrolyte further comprises one or more additives. Such additives generally do not participate in the electrolytic relithiation reaction. Non-limiting examples of additives include additives that improve the conductive properties of the relithiation electrolyte. In certain embodiments, the additive is a salt comprising an alkali metal cation or alkaline earth metal cation other than lithium (preferably potassium or magnesium) and an anion compatible with the electrolytic relithiation reaction (preferably sulfate or bicarbonate).

[0307] The relithiation salt can be any lithium salt that is soluble in the relithiation electrolyte, such as LiFSI or LiTFSI.

[0308] In a most preferred embodiment, the relithiation salt is a low-cost lithium salt. Examples of low-cost lithium salts include:

[0309] Lithium salts extracted from mines, such as Li2CO3,

[0310] Lithium salts economically prepared from mined salts, such as:

[0311] ○LiHCO3, which can be prepared from Li2CO3 as shown in Example 1;

[0312] ○Li2SO4, which can be prepared from Li2CO3 as shown in Example 2;

[0313] LiOH, which can be prepared from Li2CO3 by electrolysis of LiCl, Li2SO4, or LiHCO3, or by metathesis with calcium hydroxide;

[0314] ○LiNO3, which can be prepared by treating Li2CO3 or LiOH with nitric acid;

[0315] o LiCH3COO, which can be prepared by treating Li2CO3 with acetic acid; and

[0316] oLi2C2O4, which can be prepared by treating Li2CO3 with oxalic acid.

[0317] lithium salts produced during the hydrometallurgical recovery of spent lithium batteries, including, for example, many of the salts already listed above; and

[0318] Lithium salts recovered from lithium-bearing solutions, such as geothermal brines, salt marsh brines, solutions from lithium ore processing and lithium battery recovery processes, which also contain many of the salts listed above.

[0319] In preferred embodiments, the relithiation salt is easy to purify. An example is Li2CO3, which is easy to purify due to its low solubility (impurities precipitate out of solution while remaining dissolved) and easy to dry due to its low hygroscopicity (unlike LiCl, which is more difficult to purify due to its high solubility in water and difficult to dry due to its high hygroscopicity).

[0320] In a preferred embodiment, the relithiation salt is LiCO3, LiHCO3, LiOH, LiNO3, LiOH, Li2SO4, LiCH3COO, LiFSI, LiTFSI or Li2C2O4 or a mixture thereof, preferably the relithiation salt is LiHCO3, Li2SO4 or a mixture thereof, preferably the relithiation salt is Li2SO4.

[0321] In certain embodiments, where the relithiation solvent is water, the relithiation salt may advantageously be a water-soluble relithiation salt. In preferred embodiments, the relithiation salt is a water-soluble relithiation salt having a water solubility greater than that of LiHCO3. Non-limiting examples of such salts include: LiNO3, Li2SO4, and LiCH3COO. Converting Li2CO3 to these salts may have certain advantages over using Li2CO3 as LiHCO3. For example, electrolytic relithiation cells can be operated at higher temperatures (because the solubility of these salts increases with increasing temperature, unlike LiHCO3), which, together with their higher solubility, can facilitate operation of the electrolytic cell at higher current densities (higher cell yields and lower investment costs).

[0322] In certain embodiments, the relithiation salt is generated in situ, that is, in an electrolytic relithiation cell. In such embodiments, the method comprises adding a lithium precursor and a reagent to the electrolytic relithiation cell, reacting the lithium precursor with the reagent to form the relithiation salt. In preferred embodiments, the lithium precursor and the reagent can be added to a salt formation compartment of the electrolytic relithiation cell, the salt formation compartment being in fluid communication with a main compartment of the electrolytic relithiation cell; wherein the main compartment comprises the relithiation cathode and the relithiation anode.

[0323] In certain embodiment variations, only the relithiation salt is added to the electrolytic relithiation cell. This means that the relithiation salt is prepared prior to being added to the electrolytic relithiation cell. In such embodiments, the method may include the steps of reacting a lithium precursor and a reagent in a separate reactor to obtain the relithiation salt, and then adding the relithiation salt to the electrolytic relithiation cell.

[0324] In all cases, the choice of lithium precursor and reagent will of course depend on the desired relithiation salt. For example, LiHCO3, Li2SO4, LiNO3, and LiCH3COO can be prepared by reacting Li2CO3 with CO2, H2SO4, nitric acid, or acetic acid, respectively. In such embodiments, the lithium precursor is therefore Li2CO3, LiOH, or a mixture thereof, as desired. Similarly, in such embodiments, the reagent is therefore the acid form of CO2, H2SO4, nitric acid, acetic acid, oxalic acid, or a sulfonyl imide salt, or a mixture thereof, as desired. In a preferred embodiment, the lithium precursor is Li2CO3. In a preferred embodiment, the reagent is CO2, H2SO4, or a mixture thereof. In a more preferred embodiment, the reactant is CO2. In an alternative preferred embodiment, the reagent is H2SO4.

[0325] Notably, when LiHCO3 is used as the relithiation salt, the anode reaction in the relithiation cell produces CO2, which can be reused to produce more LiHCO3 from Li2CO3.

[0326] It is also worth noting that when Li2CO3 is used as the lithium precursor for a lithium electrolyte that contains a salt such as LiNO3, Li2SO4 or LiCH3COO as a relithiation salt, there is no need to add acid to compensate for the H+ ions consumed during carbonate conversion because the H+ ions are regenerated at the anode.

[0327] In certain embodiments, the electrolytic relithiation reaction is performed by adjusting the cell potential between the relithiation anode and the relithiation cathode or between the relithiation cathode and a reference electrode.

[0328] In certain embodiments, the electrolytic relithiation reaction is performed by regulating the cell current. In certain embodiments, under the regulated current mode, the electrolysis reaction can be performed in direct mode, pulse mode, whether the pulse mode is simple (unidirectional) mode or reverse mode. Similarly, under the regulated current mode, the electrolysis reaction can be performed at a fixed frequency or a variable frequency.

[0329] Relithiation with a reducing agent

[0330] In certain embodiment variations, step a″) comprises performing a relithiation reaction as described in WO 2021 / 092692, which is incorporated herein by reference.

[0331] In a preferred embodiment, the method comprises (i) adding the partially or fully delithiated intercalation material to a solution containing a reducing agent and a relithiating salt in a solvent; thereby enabling the partially or fully delithiated intercalation material to be relithiated and producing the relithiated lithium intercalation material. The reaction is as follows:

[0332] 2Li + +2R-Fe 2+ +2FePO4→2LiFePO4+2R′-Fe 3+

[0333] (wherein R and R' are anionic molecules or complexing agents).

[0334] In certain embodiments, the method further comprises (ii) separating the relithiated lithium intercalation material from the solution; and preferably (iii) electrochemically treating the solution separated in step (ii) to regenerate the reducing agent.

[0335] The relithiation salt is as described in the previous section.

[0336] In certain embodiments, the reducing agent is the reducing element of a redox couple having a redox potential lower than the redox potential of the partially or fully delithiated intercalation material.

[0337] According to one embodiment, the redox couple comprises, for example, a Fe(III) / Fe(II) complex, for example, selected from [Fe(CN)6] 3- / Fe(CN)6] 4- 、[Fe(nta)] / [Fe(nta)] - 、[Fe(tdpa)] 2- / Fe(tdpa)] 3- , [Fe(edta)] - / [Fe(edta)] 2- , [Fe(citrate)] / [Fe(citrate)] - , [Fe(III)-TEA] / [Fe(II)-TEA] and [Fe(oxalate)] + / [Fe(oxalate)].

[0338] According to one embodiment, step (i) furthermore comprises a step of deoxygenation of the solution.

[0339] In one embodiment, steps (i) and / or (iii) are performed in the absence of oxygen.

[0340] In one embodiment, the method further comprises the step of adjusting the pH of the solution to a pH suitable for the electrochemically active material of step (i) (eg for FePO 4 , the pH is adjusted to between 5 and 9, preferably between 6 and 7.5).

[0341] In another embodiment, the solvent is an aqueous solvent.

[0342] According to one embodiment, step (iii) of the electrochemical treatment is performed in an electrolytic cell by passing electricity between at least one cathode and at least one anode. The reaction involved in step (iii) is as follows:

[0343] Cathode reaction: 2R-Fe 3+ +2e - →2R′-Fe 2+

[0344] Anode reaction: 2OH - -2e - →1 / 2O2+H2O

[0345] In one embodiment, the electrolytic cell comprises at least one ionic or non-ionic membrane installed between the anode and the cathode to protect the regenerated reducing agent. In another embodiment, the electrolytic cell further comprises a system enabling the solution to be maintained deoxygenated, for example, the system comprises maintaining a gas such as carbon dioxide, nitrogen or argon in the absence of oxygen in the electrolytic cell.

[0346] In certain embodiments, step (iii) is performed by adjusting the cell potential between the anode and the cathode or between the cathode and a reference electrode.

[0347] In certain embodiments, step (iii) is performed by regulating the cell current. In certain embodiments, under the regulated current mode, the relithiation reaction can be performed in direct mode, pulse mode, whether the pulse mode is a simple (unidirectional) mode or a reverse mode. Similarly, under the regulated current mode, the relithiation reaction can be performed at a fixed frequency or a variable frequency.

[0348] Use of the current collector and / or pre-lithiated electrode with lithium metal or its alloy produced in step b)

[0349] The current collector and pre-lithiated electrode with lithium metal or its alloys produced in step b) can be used for many different purposes.

[0350] In certain embodiments, a current collector or pre-lithiated electrode having lithium metal or its alloys is used as:

[0351] The negative electrode in a primary or secondary lithium battery (preferably a lithium-ion battery or an all-solid-state battery),

[0352] a source of lithium metal or its alloys for pre-lithiation of the electrode material, and

[0353] Sources of lithium metal or its alloys for use in energy storage systems.

[0354] In certain embodiments, a current collector having lithium metal or its alloys is used as a source of lithium metal or its alloys for preparing the organolithium compound.

[0355] In certain embodiments, the current collector having lithium metal or its alloy is rolled to change its morphology, density, or thickness. Rolling can be performed by cold rolling at room temperature or higher. If the rolling temperature is above the melting point of lithium, a substrate with a high affinity for lithium can be used. Non-limiting examples of such substrates include silicon, tin, zinc, aluminum, ZnO, Cu2O, CuO, and Cr2O3.

[0356] In certain embodiments, a current collector comprising lithium metal or its alloys is processed to have a 3D structure, which can be used to improve the electrochemical properties of the lithium layer in a battery or increase the reaction rate when used to prepare an organolithium compound.

[0357] In certain embodiments, a current collector comprising lithium metal or its alloys is surface treated to improve its electrochemical performance in a battery. For example, a thin layer of an element such as zinc, aluminum, or one of their alloys can be deposited on the lithium layer. Various deposition methods can be used, such as physical vapor deposition (PVD) or spraying.

[0358] In other embodiments, a current collector having lithium metal or its alloy is used to produce an organolithium compound. In such preferred embodiments, it is reacted with a reagent such as an alkyl halide to produce an organolithium compound. Such compounds are important reagents used as polymerization initiators in the production of elastomers, or as strong alkaline reagents in the synthesis of organic and pharmaceutical molecules. For example, 1-chlorobutane dissolved in an organic solvent such as cyclohexane can be reacted with electrolytically deposited lithium metal or its alloy to produce n-butyllithium. In a more specific embodiment, the method further comprises the following steps: preferably in roll-to-roll mode, the current collector having the lithium metal or its alloy produced in step b) is transferred to a separate reactor, in which the electrolytically deposited lithium metal or its alloy is reacted with a reactant to produce the organolithium compound.

[0359] The lithium electrode produced by the above method

[0360] The present invention likewise relates to a lithium electrode comprising a current collector as described above with lithium metal or an alloy thereof (that is to say as produced by the method described above).

[0361] The present invention also relates to a lithium battery comprising such a lithium electrode. In a preferred embodiment, the lithium battery is a lithium ion battery or an all-solid-state battery.

[0362] definition

[0363] The terms “a” and “an” and “the” and similar referents used in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.

[0364] Unless otherwise specified, the terms "including," "having," "comprising," and "containing" are to be construed as open terms (that is, meaning "including but not limited to"). On the other hand, the expression "consisting of excludes any unspecified elements, steps, ingredients, etc. The expression "consisting essentially of limits the scope to the specified materials or steps, as well as those that do not materially affect the basic and novel characteristics of the invention.

[0365] Recitation of ranges of values ​​herein is intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All subsets of values ​​within the range are also incorporated into the specification as if they were individually recited herein.

[0366] All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context.

[0367] The use of any and all examples, or exemplary language (eg, "such as") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise indicated.

[0368] No language in the specification should be construed as indicating any non-claimed element as not essential to the practice of the invention.

[0369] As used herein, the term "about" has its ordinary meaning. In certain embodiments, it may mean plus or minus 10% or plus or minus 5% of a qualified value.

[0370] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0371] Further objects, advantages and features of the present invention will become more apparent from the following non-limiting description of specific embodiments of the invention, given by way of example only with reference to the accompanying drawings.

[0372] Description of Illustrative Embodiments

[0373] The present invention is illustrated in more detail by the following non-limiting examples.

[0374] Example 1 - Apparatus for carrying out the method of the invention using in situ generated LiHCO3 as the relithiation salt A schematic diagram of an embodiment of the method of the invention is shown in FIG. Figure 1 shown.

[0375] The electrolytic relithiation reaction is carried out in an electrolytic relithiation cell (10) containing a relithiation electrolyte and equipped with a stirrer (12). Figure 1 In the embodiment, the relithiation electrolyte comprises LiHCO 3 as the relithiation salt.

[0376] This relithiation salt, LiHCO3, is produced in an electrolytic relithiation cell (10) by reacting a lithium precursor, namely Li2CO3 powder (14), with a reagent, in this case CO2, which is added to the electrolyte using a bubbler (16). A wall (18) divides the electrolytic relithiation cell (10) into a salt-forming compartment (20) and a main compartment (22), each of which is fluidically connected to the other.

[0377] The main compartment (22) of the electrolytic relithiation cell (10) contains a relithiated anode (24) and a partially or fully delithiated intercalation material (26) that serves as a relithiated cathode. After the electrolytic relithiation reaction, the partially or fully delithiated intercalation material (26) is relithiated to form a relithiated lithium intercalation material (28). In the present example, LiFePO4 (LFP) on a metal foil is used as the intercalation material, which is partially or fully delithiated and relithiated.

[0378] This step is performed in a roll-to-roll configuration. Thus, partially or fully delithiated intercalation material (26) supplied from a roll (30) is introduced into an electrolytic relithiation cell (10), and relithiated lithium intercalation material (28) is extracted from the electrolytic relithiation cell (10) and collected on a roll (32) with the help of intermediate rolls (34, 36, 38, and 40). A series of washing, rinsing, dehydration, and drying steps may be included in the roll-to-roll unit.

[0379] As indicated by arrow B, the roll (32) of relithiated lithium intercalation material (28) is transferred to a production electrolytic cell (42). The production electrolytic cell (42) uses the relithiated intercalation material (28) as a production anode, a current collector (44) as a production cathode, and a production electrolyte. In the present example, the current collector (44) is a treated or untreated copper foil.

[0380] In the production electrolytic cell (42), lithium is electro-deposited on the current collector (44), thereby producing a lithium-coated current collector (46), and the relithiated lithium intercalation material (28) is (partially or completely) delithiated, thereby regenerating the lithium intercalation material (28). As indicated by arrow A, the lithium intercalation material (28) can then be returned to the electrolytic relithiation cell (10) for relithiation.

[0381] This step is also performed in a roll-to-roll configuration. Relithiated lithium intercalation material (28) is fed from roll (32), and partially or fully delithiated intercalation material (26) is collected on roll (30) with the help of intermediate rolls (48, 50, 52, and 54). Similarly, current collector (44) is fed from roll (56), and lithium-coated current collector (46) is collected on roll (58) via intermediate rolls (60, 62, and 64). A series of washing, rinsing, dehydration, and drying steps can be included in the roll-to-roll unit.

[0382] The lithium-coated current collector (46) can be used or processed in various ways. Arrow C shows that the coil (58) of the lithium-coated current collector (46) can be cold rolled using cold rolling rollers (60) to form a cold-rolled lithium-coated current collector (62), which is collected on a coil (64) by intermediate rollers (66, 68). Arrow D shows that the coil (58) of the lithium-coated current collector (46) can be hot rolled by hot rolling rollers (70) to form a hot-rolled lithium-coated current collector (72), which is collected on a coil (74) by intermediate rollers (76, 78).

[0383] exist Figure 1 In the figure, the intercalation material used in the lithium generation step is LiFePO4 (LFP) on an aluminum substrate. The resulting delithiated intercalation material (FP in this figure) is returned to the relithiation step to undergo relithiation in an aqueous medium in a cathode reaction, where oxygen is released as an anodic reaction, as shown below:

[0384] Reaction 1 (cathode reaction): 2Li + +2e - +2FePO4→2LiFePO4

[0385] Reaction 2 (anode reaction): 2HCO3 - →1 / 2O2+H2O+2CO2+2e -

[0386] In this case, the source of lithium ions is the Li2CO3 dissolved in water as LiHCO3 by bubbling CO2 into a suspension of Li2CO3 in water according to the following reaction:

[0387] Reaction 3: Li2CO3+CO2+H2O→2LiHCO3

[0388] The advantage of dissolving Li2CO3 in the form of LiHCO3 is that the solubility of LiHCO3 is higher than that of Li2CO3.

[0389] Example 2 - Apparatus for carrying out the method of the invention using in situ generated Li2SO4 as the relithiation salt

[0390] Figure 2 A further embodiment of the method of the invention is shown, which is based on the conversion of Li2CO3 into Li2SO4. Figure 2 and Figure 1 Very similar, except that there is no bubbler and the relithiation electrolyte in the electrolytic relithiation cell (10) is also different. In this case, the source of lithium ions is dissolved in water as Li2SO4 by reacting Li2CO3 with H2SO4 acid according to the following reaction:

[0391] Reaction 6: Li2CO3+H2SO4→Li2SO4+CO2+H2O

[0392] The cathode reaction is the same as in the case of the electrolyte with LiHCO3 base (Example 1). However, in the anode reaction, in addition to the release of oxygen, H + ions, which helps in the regeneration of H2SO4 required to convert Li2CO3 into Li2SO4

[0393] Reaction 7 (cathode reaction): 2Li + +2e - +2FePO4→2LiFePO4

[0394] Reaction 8 (anode reaction): H2O-2e - →1 / 2O2+2H +

[0395] Therefore, when Li2CO3 is added to the dedicated compartment of the electrolytic relithiation cell, H + ions, there is no need to add acid to the solution during the continuous addition of Li2CO3 powder to the cell.

[0396] Example 3: Roll-to-roll electrodeposition cell

[0397] Figure 3 A further embodiment of an apparatus for carrying out the method of the present invention is shown. In this case, the electrodeposition of lithium (step b) is carried out in a roll-to-roll configuration. One of the advantages of the present invention is that no membrane is present in the production electrolysis cell (42), which makes it possible to use a multi-stage electrolysis configuration, which is difficult to achieve if the lithium electrolysis cell must have separate anolyte and catholyte compartments, as described in US 2021 / 0381115 A1 and US 2022 / 0367874 A1.

[0398] exist Figure 3 In the embodiment of the present invention, two rolls (32) feed the relithiated lithium intercalation material (28) to the production electrolytic cell (42). Similarly, two rolls (30) collect the partially or completely delithiated intercalation material (26). This is accomplished by a number of intermediate rolls (76). In addition, the current collector (44) is fed from the roll (56), and the lithium-coated current collector (46) is collected on the roll (58) by the intermediate roll (78) and the pair of calendaring rolls (80).

[0399] The cell is also equipped with several pairs of calendering rollers that densify the lithium metal layer during electrodeposition while still submerging it in the electrolyte. This also minimizes the inclusions in the lithium film and increases its purity.

[0400] Example 4: Thin Film Electrodeposition of Lithium in a Bag Cell

[0401] In a bag cell assembly, LFP was used as a lithium ion source to electrolytically deposit a thin film of lithium on an ultra-thin current collector. A lithium layer with a thickness of approximately 11.5 μm was confirmed.

[0402] A thin film of lithium metal is obtained by electrodeposition in a lithium double salt electrolyte dissolved in a solvent with a carbonate base. The electrolyte solution is prepared by mixing ethylene carbonate (EC) with diethyl carbonate (DEC) in a 50 / 50 volume ratio in an argon-filled glove box. Next, lithium trifluoromethanesulfonate (LiCF3COO) and lithium bis(fluorosulfonyl)imide (LiFSI) are added to the solvent mixture at concentrations of 0.9M and 0.1M, respectively. The suspension is vigorously stirred until the salt is completely dissolved. To ensure the stability of the electrolyte with the lithium metal and to eliminate any trace water, a small strip of bare lithium metal is immersed in the electrolyte for at least 24 hours before use.

[0403] LiFePO4 anode (LFP) was prepared by mixing carbon-coated pristine LFP with conductive carbon materials (carbon fibers (VGCF-H) and carbon black (Denka black)) and polymer binder (polyvinylidene fluoride (PVDF)) in a weight ratio of 91:2.5:2.5:4. The mixture was dispersed in N-methyl-2-pyrrolidone (NMP) in a planetary centrifugal mixer until a completely homogeneous suspension was obtained. The suspension was coated on a 15 μm thick carbon-coated aluminum foil using a doctor blade and dried at 80°C for 24 h. The coating was densified by roller calendering. The total specific charge of the electrode was 10 mg / cm 2 .

[0404] Lithium electrodeposition was performed in a bag cell under constant current conditions. The cell was assembled using a 4.5 μm thick dried copper foil as the cathode, the previously mentioned LFP applied to aluminum foil as the anode, and a polypropylene (PP) film (Celgard 3501) as the separator. The active specific surface area of ​​the two electrodes was 25.5 cm 2 The bag cell was filled with the previously prepared electrolyte, sealed under vacuum, and mounted between press plates, thereby compressing the bag cell to about 75 psi. Galvanostatic electrolysis was performed at 0.5 mA / cm at 25°C for a total charge of about 129 C passed. 2 The applied current and response potential of this plating sequence are as follows: Figure 4 shown.

[0405] Once electrodeposition is complete, the lithium cathode is recovered by opening the bag cell in a dry room hood. The copper / lithium electrode is washed three times with tetrahydrofuran (THF) and once with dimethoxyethane (DME). The solvents used are all anhydrous solvents. The lithium is then rolled between two stainless steel rollers at a speed of 10 mm / s at room temperature while the electrode is placed between the following 11 μm copper foil and a 20 μm polypropylene (PP) foil (another 11 μm copper foil on top) to protect the integrity of the lithium. The rolled lithium is placed in a vacuum for 12 hours to ensure that DME is completely evaporated. The resulting electrode thin foil is composed of a lithium layer having a thickness of approximately 11.5 μm on a 4.5 μm copper foil.

[0406] Example 5: Relithiation of LFP anode

[0407] In this example, a delithiated LFP (FP) electrode obtained from a button cell was used to deposit lithium under conditions similar to those of Example 4 and then relithiated in an aqueous Li2SO4 electrolyte. It was confirmed that this resulted in complete relithiation of the electrode in aqueous medium.

[0408] The initial LFP electrode used during lithium plating consisted of a 16 mm diameter disk consisting of a mixture of LFP, conductive carbon, and PVDF applied to a 15 μm aluminum foil as described in Example 4, with an active loading of 9.1 mg / cm 2 Considering that the theoretical capacity of LFP is 170 mAh / g, the charge capacity of the LFP anode is 3.02 mAh. Next, in the double salt electrolyte described in Example 4, the charge capacity of the LFP anode was 3.02 mAh. 2 The LFP anode was discharged onto a 4.5 μm copper foil cathode at a constant current of 1.5 Å for 1.29 h, resulting in lithium electrolytic deposition in a CR2032 coin cell. Figure 5 The potential evolution over time recorded during electrolysis is shown. The total charge through the cell was 2.6 mAh. In this respect, based on Coulomb calculations, the LFP electrode was discharged by 86%.

[0409] In the second step, the delithiated LFP electrodes (referred to as FP electrodes) were recovered from the button cell and rinsed three times in THF, once in hexane, and then dried before relithiation. The FP electrodes were assembled on a 1 cm 2 The FP electrode was relithiated by placing a 0.25 M LiSO solution in a lithium sulfate electrolyte. A 0.25 M LiSO solution was prepared from ACS-grade lithium sulfate and demineralized water and adjusted to pH 6 with dilute HSO. A constant potential of -0.05 V compared to NHE was applied between the cathode and a Ag / AgCl reference electrode (3.5 M KCl). After one hour, a total charge of 1.77 mAh had passed through the FP electrode. Figure 6 The change of accumulated charge over time is shown in Figure 2. The conversion degree of the electrode before and after relithiation (from FP to LFP) was confirmed by X-ray diffraction (XRD) analysis, as shown in Figure 2. Figure 7 The spectrum of the electrode before relithiation shows a 12.5% ​​partially delithiated electrode, which is consistent with the Coulometric electrodeposition data of lithium. The spectrum of the electrode after relithiation is similar to that of the pristine LFP, confirming the complete relithiation of the electrode.

[0410] Example 6: Electrochemical characteristics of electrodeposited lithium

[0411] The lithium-coated copper foil electrode produced in Example 4 was used as the negative electrode in a rechargeable lithium battery. It was confirmed that the coin cell prepared with electrodeposited lithium exhibited significantly higher charge-discharge stability than that of a cell prepared with commercially available ultrathin lithium foil prepared by PVD.

[0412] First, a lithium anode disk with a diameter of 14 mm was punched out between two PP foils of the rolled lithium obtained in Example 4.

[0413] By using Thinky TM Centrifugal mixer Li(Ni 0.8 ,Mn 0.1 ,Co 0.1 The cathode was prepared by mixing 2% PO (NMC811), PVDF, DENKA black, and graphite in NMP at 94% w / w, 3% w / w, 2% w / w, and 1% w / w, respectively. The resulting suspension was then applied to carbon-coated aluminum. The coating was dried at 130°C and laminated to a density of 3.3 g / cm 3 The resulting cathode foil was then dried again under vacuum at 120°C for 12 hours.

[0414] A 14 mm diameter disc was punched from the cathode foil and mounted in a stainless steel CR2032 coin cell. The rolled lithium cathode and anode were separated by a Celgard 3501 membrane. The cell was filled with 60 μl of 1.7 M LiFSI salt dissolved in a DME-TTE mixture (molar ratio 1.2:3). Two cells were generated in this manner.

[0415] The cell was cycled at 25°C for three formation cycles at a charge / discharge rate of C / 10 and then stability tested at a rate of C / 3. + / Li 0 , the potential limits are set to 2.7V and 4.2V.

[0416] To compare the performance of the electrolytically deposited lithium with that of commercially available ultrathin lithium foil, a reference cell was prepared using a commercially available 5 μm thin lithium foil deposited directly on copper foil by PVD as the anode. These cells were tested under the same conditions with the same NMC. Figure 8 The variation of specific capacity with charge-discharge cycles is shown.

[0417] As can be seen, the two coin cell cells prepared with electrolytically deposited lithium exhibited charge-discharge stability significantly higher than the charge-discharge stability of the two cells prepared with the previously described commercially available ultrathin lithium foil prepared by PVD.

[0418] Example 7: Electrodeposition of Thin Lithium on Copper Foil in an Electrochemical Cell Without a Membrane

[0419] An integral beaker-type electrochemical cell (with no separator between the cathode and anode compartments) was used. The lithium thin film is electrolytically deposited on a copper foil (cathode) using a Tait cell (SI). The resulting lithium is then used as the negative electrode of a rechargeable lithium battery. It has been demonstrated that the method of the present invention can be implemented under the following conditions: 1) in an electrochemical cell without a membrane, and 2) at a high current density (4 mA / cm2 )Down.

[0420] More specifically, the cell consists of a bottom plate on which a flat cathode made of 4.5 μm copper foil is placed, a glass tube (internal diameter 6.5 cm) placed on the copper foil, and a top plate on which the assembly is firmly fixed in place by long screws with nuts. The seal between the copper foil and the glass body is ensured by a gasket.

[0421] Electrodeposition was performed in an argon-filled glove box (H2O < 0.1 ppm; O2 < 0.1 ppm) using an electrolyte solution consisting of ethylene carbonate (EC) and diethyl carbonate (DEC) in a 50 / 50 volume ratio, and lithium trifluoromethanesulfonate (LiCF3COO) and lithium bis(fluorosulfonyl)imide (LiFSI) at concentrations of 0.6 M and 0.4 M, respectively. 2 The stainless steel disc was covered with an LFP-based slurry of the same formulation as described in Example 4, with an active material loading of 23 mg / cm 2 The anode was mounted on the stirring shaft and positioned 0.6 cm from the cathode foil. A volume of 20 ml of electrolyte with carbonate base was added to the cell. The active cathode surface was 25.5 cm 2 The electrolysis was carried out at room temperature with a constant current at an anode speed of 50 rpm and a current of 4 mA / cm 2 The reaction was carried out at a constant current density of 1.5 Å for 22 minutes. Figure 9 The change in cell potential over time is shown.

[0422] The resulting electrodeposited lithium was cleaned and rolled using the same procedures as in Example 4 before thickness measurement, which revealed a lithium thickness of approximately 9 μm. The appearance of the deposit before and after rolling is shown in FIG. Figure 10A and Figure 10B In, Figure 11 Shown is a cross-section of rolled lithium under a scanning electron microscope.

[0423] The resulting lithium is then used as the negative electrode of a rechargeable lithium battery. First, a lithium anode disc with a diameter of 14 mm is cut between two PP foils of rolled lithium.

[0424] By using Thinky TM The cathode was prepared by mixing LFP with PVDF, DENKA black, and graphite in NMP at ratios of 89% w / w, 5% w / w, 3% w / w, and 3% w / w, respectively, using a centrifugal mixer. The resulting suspension was then applied to carbon-coated aluminum and dried at 120°C. The resulting cathode foil was then dried again at 120°C under vacuum for 12 hours.

[0425] 14 mm diameter discs were cut from the cathode foil and mounted in stainless steel CR2032 coin cell cells. The rolled lithium cathode and anode were manufactured by Celgard TM The cell was filled with 60 μL of 1.7 M LiFSI salt dissolved in a DME-TTE mixture (molar ratio 1.2:3).

[0426] The cell was cycled at 25°C for one formation cycle at a charge and discharge rate of C / 24, then two additional formation cycles at a rate of C / 10, and finally cycled at a discharge rate of 1C and a charge rate of C / 3 for stability testing. + / Li 0 , the potential limits are set to 2V and 4V. Figure 12 The cycling stability of the obtained lithium was compared with that of lithium foil prepared by PVD.

[0427] Example 8: Electrodeposition of Lithium Thin Film on Treated Copper Foil in an Electrochemical Cell Without a Membrane

[0428] To improve lithium deposition, electrodeposition of lithium thin films was performed on different types of foils.

[0429] Deposition was performed using the same experimental setup as in Example 7 (cell without membrane, one rotating anode coated with LFP and the same electrolyte formulation).

[0430] The electrochemical characteristics of each lithium obtained were compared with a commercially available lithium PVD cathode according to Example 7. Figure 13 The cycling stability of each sample is shown. The performance of the electrodeposited lithium is better than or close to that of the PVD lithium.

[0431] Example 8.1: Copper-Silver Substrate

[0432] A cathode consisting of a 9 μm thin copper foil coated with a thin layer of silver was prepared. The silver coating was prepared by washing the copper foil in acetone, immersing the foil in 1 M sulfuric acid for 1 minute at room temperature, rinsing off the acid with water, and finally immersing the clean copper foil in an electroless silver plating solution for 10 seconds. The resulting treated current collector was then dried and used as the current collector in the cell described in Example 7 without a membrane. The applied current was 4 mA / cm 2 , lasting 22 minutes, with an active cathode surface area of ​​25.5 cm 2 The evolution of the cell potential over time is shown in Figure 14 Prior to thickness measurement and electrochemical cycling, the resulting electrodeposited lithium was cleaned and rolled using the same procedures as in Example 7, which revealed a lithium thickness of approximately 6.5 μm.

[0433] Example 8.2: Brass Foil Substrate

[0434] Brass foil was used to demonstrate the lithiophilic nature of this alloy. The foil was a commercially available brass foil consisting of 68% w / w copper and 32% w / w zinc. After cleaning with acetone and adequate drying, the 20 μm brass foil was used as the cathode in a lithium electrodeposition cell under conditions similar to those described above for the silver-plated copper foil. The evolution of the cell potential with time is shown in Figure 15 Prior to thickness measurement and electrochemical cycling, the resulting electrodeposited lithium was cleaned and rolled using the same procedures as in Example 7, which revealed a lithium thickness of approximately 12 μm.

[0435] Example 8.3: 3D textured nickel foil substrate

[0436] Lithium electrodeposition was performed on commercially available textured nickel foil. The foil has a raised surface area due to the nickel dendrite formation of its 3D texture. The 3D foil was used as a cathode substrate in a manner similar to that of the previous examples. Deposition was performed under the same conditions as for the copper-silver or brass foil. The evolution of the cell potential over time is shown in Figure 16 Prior to thickness measurement, the resulting electrodeposited lithium was cleaned and rolled using the same procedures as in Example 7, which revealed a lithium thickness of approximately 9 μm.

[0437] Example 9: Electrodeposition of Thin Lithium on Metallized Polymers in a Membrane-Free Electrochemical Cell

[0438] The metallized polymer was used as an electrodeposition substrate and the results showed that this substrate can be used successfully.

[0439] The metallized polymer consisted of a 50 μm thick polyethylene terephthalate film coated with a thin copper film deposited by physical vapor deposition (PVD).

[0440] Lithium electrodeposition was carried out using the same electrolyte and configuration as in Example 8.2. 4 mA / cm 2 The current density lasted for 13 minutes.

[0441] The evolution of the cell potential over time is shown in Figure 17 The obtained lithium foil is shown in Figure 18 middle.

[0442] Example 10: Relithiation of the delithiated LFP anode of the above Tait cell

[0443] The delithiated LFP (FP) electrode produced by anodic discharge of LFP during lithium electrodeposition on a brass substrate as described in Example 8.2 was deposited on a LiHCO 3The relithiation was carried out in an aqueous electrolyte. The relithiated electrode was then used to generate lithium. Complete relithiation of the electrode and its successful reuse for lithium generation were confirmed.

[0444] The initial LFP electrode used during lithium plating in Example 8.2 consisted of a 20 mm thick 25 cm 2 The stainless steel disc was coated with a mixture of LFP, conductive carbon and PVDF with an active loading of 22.4 mg / cm 2 .

[0445] Considering that the theoretical capacity of LFP is 170 mAh / g, the charge capacity of the LFP anode is 97 mAh. The total electrodeposited charge is 36.7 mAh, which corresponds to a delithiation degree of about 38% of the LFP anode. The evolution of the cell potential with time is shown in Figure 19 middle.

[0446] The delithiated LFP electrode (referred to as the FP electrode) was recovered from the cell of Example 8.2 and rinsed three times in THF, once in hexane, and then dried before relithiation. The FP electrode was mounted on a stirrer and immersed in a 0.5 M LiHCO3 solution at a near-neutral pH. This electrolyte was prepared from ACS grade lithium carbonate by dissolving the lithium salt in demineralized water in a pressurized reactor under a CO2 partial pressure of 2 atm. 25 cm 2 A platinum-coated titanium mesh was used as the anode. 4 mA / cm was applied between the cathode and the anode. 2 The cathode potential was monitored with an Ag / AgCl reference electrode (KCl 3.5 M at 0.198 V vs. NHE) immersed just next to the cathode. The current ceased when the cathode potential dropped below -0.5 V vs. NHE, indicating a high degree of lithiation (after 21 minutes).

[0447] The accumulated coulomb charge corresponds to 34.3 mAh. Figure 19 The current density and cathode potential change with time. Figure 20 As shown, FTIR confirmed the relithiation of the electrode. Therefore, the spectra of the electrode before and after relithiation correspond to the partially delithiated and fully lithiated states of LFP, respectively. The spectrum of the electrode after relithiation is similar to that of the pristine LFP, confirming complete relithiation of the electrode.

[0448] The previously relithiated LFP electrode was reused as the anode in a second lithium electrodeposition. The electrochemical conditions were similar to those used in Example 7. Figure 21 The evolution of the cell potential shown is similar to the evolution of the cell potential obtained in Example 8.2, thus confirming the possibility of reusing the same LFP anode after the aqueous relithiation step.

[0449] Example 11: Relithiation of LTO anode in aqueous solution

[0450] This example shows that the LTO electrode (Li4Ti s O 12 ) in aqueous solution. Complete relithiation has been confirmed.

[0451] The LTO-based anode, consisting of a thin layer of LTO applied on aluminum / carbon foil, was electrochemically relithiated in an aqueous electrolyte. The electrolyte consisted of an aqueous solution of 25 M LiFSI and 25% v / v dimethoxyethane, adjusted to pH 8 with 2 M LiOH. 2 A piece of LTO coated foil was glued to the glass pattern to make the working electrode. A square mask of PVDF tape was applied to cover the edges of the working electrode, leaving 3.5 cm 2 The active area of ​​the counter electrode is exposed to the electrolyte solution. 2 4mA / cm was applied between the cathode and the anode. 2 The current was kept for 60 minutes, while the potential of the working electrode was monitored by a platinum pseudo-reference electrode. The evolution of the working electrode potential is shown in Figure 22 middle.

[0452] Once relithiated, the working electrode was rinsed with ethanol and dried at 60°C for several minutes. Relithiation was demonstrated by performing linear sweep anodic voltammetry in the same electrolyte and using the same experimental setup. In this regard, the potential of the working electrode was swept from 0 V relative to the VCO to 1.2 V relative to the reference electrode at a sweep rate of 0.1 V / s. Figure 23 The resulting voltammogram shown shows a large oxidation peak at -0.357 V relative to Pt, corresponding to Li4Ti5O 12 Li7Ti5O 12 oxidation.

[0453] Example 12: Additives for Thin Lithium Electrodeposition

[0454] Additives can be added to the electrolyte to improve the appearance and properties of lithium thin films. With this in mind, various additives have been tested to improve lithium properties. The use of these additives has been shown to promote lithium electrodeposition.

[0455] The experiment consisted of lithium electrodeposition in a coin cell using a 4.5 μm thick copper foil with a diameter of 16 mm as the cathode, covered with a 50 μm thick polypropylene mask with an inner diameter of 8 mm. This mask allowed the deposition to be simulated in an electrochemical cell without a membrane by moving the two electrodes apart, creating a gap between the cathode and the membrane. The anode consisted of an aluminum foil coated LFP membrane, as described in Example 7. Deposition was performed at 4 mA / cm 2 The current density was maintained for 10 minutes.

[0456] A series of additives were added to an alkaline electrolyte consisting of 50 / 50 EC and DEC and LiCF3COO and LiFSI electrolyte salts at concentrations of 0.6 M and 0.4 M, respectively. Figure 24 It can be seen that the potential peak of the initial nucleation phase decreases after adding 0.2M VC, 0.01M LiDFOB, or 0.1M CsPF6. This will translate into a more uniform coverage of the surface of the copper substrate during lithium electrodeposition.

[0457] Example 13: Synthesis of n-butyllithium from electrodeposited lithium

[0458] Lithium obtained by electrodeposition was successfully used to synthesize the commonly used organometallic n-butyllithium.

[0459] For this reason, on a 4.5 μm thick copper substrate, for 1.44 mAh / cm 2 The total charge, at 0.5 mA / cm 2 Initial electrodeposition was performed in a coin cell at a current density of 100 nm. After electrodeposition, the resulting lithium electrode with a diameter of 16 mm was recovered from the coin cell in an argon-filled glove box, cleaned of electrolyte residues with THF, subsequently rinsed with DEC, and dried in a drying chamber at 25°C under vacuum overnight.

[0460] In order to evaluate the formation efficiency of n-Butyllithium, a titration curve was drawn to accurately measure the concentration of the n-Butyllithium in n-hexane. Therefore, the n-Butyllithium dilution solutions of four different concentrations (0.005M / L, 0.0vM / L, 0.015M / L and 0.025M / L) were prepared using commercially available 1.6M / L solution. A saturated solution of n-phenanthroline in a mixture of n-hexane and toluene of 25 μL volumes was added to the n-Butyllithium solution previously prepared by 2ml. The 2% v / v dilution solution of 2-propanol in n-hexane was used as titrant and was added dropwise to a bright yellow endpoint. The volumetric concentration of the titrant solution relative to the sample solution was drawn for the calculated concentration of each absorption n-Butyllithium solution, thereby producing R 2 For 99.99% of the straight lines, such as Figure 25 shown.

[0461] A 2% v / v dilute solution of n-butyl chloride was prepared in dry n-hexane to synthesize n-butyl lithium from the lithium deposited by electrodeposition. A subsample of 14 mm in diameter was cut from the dried lithium electrode and placed in a vial. The charge of the lithium deposit was measured at 0.78 mg. A magnetic stirrer was added to a vial containing 0.435 ml of the diluted butyl chloride solution. The flask was sealed and stirred for 15 minutes, after which the solution was transferred to a 10 ml volumetric jar. The apparatus was rinsed 3 times with n-hexane and transferred to a volumetric jar to recover any trace n-butyl lithium from the vial and solid residue. Once the instrument was filled with n-hexane, a 5 ml sample was taken out from the volumetric jar and n-butyl lithium was titrated with 2-propanol. To this end, 20 μl of a saturated n-phenanthroline solution was added to 5 ml. The deep red color obtained indicated the presence of n-butyl lithium. The propanol solution was added dropwise to a bright yellow endpoint (0.070 ml in this case). According to the titration, it was determined that 0.42 mg of lithium reacted with butyl chloride, corresponding to a reaction efficiency of 67%.

[0462] Example 14: Pre-lithiation of Lithium Insertion Anode

[0463] The following examples demonstrate the application of the above electrochemical methods to pre-lithiate lithium-intercalation anode materials in order to reduce lithium losses during formation cycles. After pre-lithiation, these lithium losses are significantly offset in graphite and SiOx anodes.

[0464] In the first case, a commercially available graphite anode was used, consisting of a lithium intercalation layer consisting of 94 wt. % synthetic graphite coated on an 8 μm copper strip. Its active mass was 6.7 mg / cm 2 , thus providing 2.27mAh / cm 2 A coin cell was assembled for pre-lithiation, comprising an electrode with a diameter of 16 mm taken from a graphite anode, a Celgard TM membrane and a positive LFP electrode (as used in Example 12). The electrolyte used corresponds to the alkaline electrolyte of Example 12. Then for 0.36 mAh / cm 2 or 0.48 mAh / cm 2 The total charge, at 0.5 mA / cm 2 These cells were charged with a constant current of 1000 Ω / min to pre-lithiate the graphite electrodes. These coulombic charges corresponded to 16% and 21% of the initial capacity of the graphite anode, respectively. The constant current curves thus obtained are shown in Figure 26 middle.

[0465] Similarly, using 81% SiO x A commercially available silicon oxide anode is made of a lithium intercalation layer consisting of 4% carbon nanotubes and 15% polyimide. The total specific capacity of the anode is 2.52 mAh / cm 2As previously described, the SiO x An electrode with a diameter of 16 mm was removed from the anode for pre-lithiation of the button cell. The applied coulombic charge was 0.75 mAh / cm 2 or 1.0mAh / cm 2 , corresponding to SiO x 30% and 40% of the total capacity of the anode. The constant current curve thus obtained is shown in Figure 27 middle.

[0466] The initial capacity loss of each pre-lithiated anode was compared with that of the original anode of its cell by electrochemical cycling on the positive LFP electrode. The galvanostatic cycling protocol at limiting potentials began with a charge-discharge formation cycle at C / 24, followed by two additional formation cycles at C / 10, and then a stability test of charge at C / 3 and discharge at 1C. For graphite, the potential limit was set between 2 V vs. lithium and 4 V vs. lithium, and for SiO x The anode potential limit is set between 2 V and 3.8 V relative to lithium. Figure 28 The cycling reversibility of the first formation cycle of the pristine graphite anode and the pre-lithiated graphite anode was compared. When the capacity loss of the pristine electrode reached 21%, the capacity loss of the pre-lithiated anode at 15% capacity dropped to 3%, while the pre-lithiated anode reached full reversibility at 20% capacity. Similarly, SiO x Pre-lithiation of the anode increases the initial capacitance loss from 68% of the pristine electrode to exactly 32% of the 30% pre-lithiated electrode and 11% of the 40% pre-lithiated electrode. Figure 29 Compared with the original SiO x Anode and pre-lithiated SiO x Cyclic reversibility of the anode first formation cycle.

[0467] The scope of the claims should not be limited by the preferred embodiments shown in the examples, but should be given the broadest interpretation consistent with the description as a whole.

[0468] References

[0469] This specification refers to many documents, the contents of which are hereby incorporated by reference in their entirety. These documents include but are not limited to the following:

[0470] · Lee et al., "Synthesis of Lithium Thin Film by Electrodeposition from Ionic Liquid", Applied Mechanics and Materials, 217 - 219, November 2012, pp. 1049 - 1052

[0471] · Porthault et al., "Electrodeposition of lithium metal thin films and its application in all - solid - state micro batteries", Electrochimica Acta, 194 (2016) 330 - 337

[0472] · Coyle et al., Recycle of End - of - Life NMC 111 Cathodes By Electrochemical Relithiation, 2019 Meet. Abstr. MA2019 - 02449

[0473] · Montoya et al., Relithiation of Cathode Materials for the Recycling of Lithium - Ion Batteries, 2019 Meet. Abstr. MA2019 - 02444

[0474] · Shi et al., Ambient - Pressure Relithiation of Degraded Li x Ni 0.5 Co 0.2 Mn 0.3 O2(0 < x < 1) for Direct Regeneration of Lithium - Ion Battery Cathodes x Ni 0.5 Co 0.2 Mn 0.3O2(0 < x < 1) via Eutectic Solutions for Direct Regeneration of Lithium-Ion Battery Cathodes), 《Advanced Energy Materials》, Volume 9, Issue 20, May 23, 2019, 1900454

[0475] · Zhou et al., Direct recovery of scrapped LiFePO4 by a green and low-cost electrochemical re-lithiation method, 《Green Chem.》, 2022, 24, 6278 - 6286

[0476] · Lahtinen et al., Reuse of LiCoO2 Electrodes Collected from Spent Li-Ion Batteries after Electrochemical Re-Lithiation of the Electrode, 《ChemSusChem》2021, 14, 1 - 12

[0477] · Zhang et al., Electrochemical Relithiation for Direct Regeneration of LiCoO2 Materials from Spent Lithium-Ion Battery Electrodes, 《ACS Sustainable Chem. Eng.》2020, 8, 31, 11596 - 11605

[0478] Holtstiege et al., Prelithiation Strategies for Rechargeable Energy Storage Technologies: Concepts, Promises and Challenges, Batteries, 2018, 4(1), 4

[0479] WO 2019 / 113534

[0480] WO 2019 / 070896 A1

[0481] WO 2017 / 095989 A1

[0482] WO 2021 / 092692

[0483] US20220328800A1

[0484] US20210091426A1

[0485] US20210381115A1

[0486] US20180040914A1

[0487] US20160351889A1

[0488] ·CN112216819B

[0489] ·CN110504451B

[0490] ·EP3358046B1

[0491] DE102018207391A1

Claims

1. A relithiated lithium intercalation material for producing lithium metal or its alloys or for prelithiating electrode materials.

2. Use of a relithiated lithium intercalation material for producing lithium metal or its alloys or for prelithiating electrode materials.

3. The material / use according to claim 1 or claim 2, which is used to produce the lithium metal or the alloy thereof, preferably to produce the lithium metal, preferably wherein the lithium metal or the alloy thereof is in the form of a film, preferably wherein the lithium metal or the alloy thereof is produced by electrodeposition.

4. The material / use according to claim 1 or claim 2, wherein the material / use is used to pre-lithiate an electrode material, preferably to pre-lithiate an anode material, more preferably to pre-lithiate graphite, silicon, silicon oxide (SiO x ), pre-lithiation of silicon-carbon composite materials, carbon nanotubes or their mixtures.

5. The material / use according to any one of claims 1 to 4, wherein the relithiated lithium intercalation material is lithium phosphate or lithium oxide, preferably: ·Li w FePO4 (wherein w≤1.1, preferably w is 1), ·Li w Fe 1-x Mn x PO4 (wherein w≤1.1, preferably w is 1; 0<x≤1, preferably 0.2<x≤0.4), ·Li w Mn2O4 (wherein w≤1.1, preferably w is 1), ·Li w Mn 1.5 Ni 0.5 O4 (wherein w≤1.1, preferably w is 1), ·Li 4+z Ti5O 12 (where 0 < z ≤ 3), or ·NMC(Li w Ni 1-x-y Mn x Co y O2, wherein w≤1.3, preferably w is 1; 0≤x≤1, 0≤y≤1, and 0≤z≤1, and M is aluminum, magnesium, titanium, niobium, zirconium, tungsten, molybdenum, yttrium, lanthanum, tantalum or a mixture thereof).

6. The material / use according to claim 5, wherein the relithiated lithium intercalation material is Li w FePO4.

7. The material / use according to any one of claims 1 to 6, wherein the relithiated lithium intercalation material has been obtained from a used electrode and then relithiated, or wherein the relithiated lithium intercalation material has been used to produce lithium metal or an alloy thereof or to prelithiate an electrode material and then relithiated.

8. The material / use according to any one of claims 1 to 7, wherein the relithiated lithium intercalation material has recovered at least 50%, preferably at least 75%, more preferably at least 85%, even more preferably at least 95% and most preferably still at least 99% of the previously deintercalated lithium ions.

9. A production anode for producing lithium metal or its alloys or for pre-lithiating an electrode material, the production anode comprising a relithiated lithium intercalation material.

10. Use of a production anode comprising a relithiated lithium intercalation material for producing lithium metal or its alloys or for pre-lithiating an electrode material.

11. Production of an anode / use according to claim 9 or claim 10, wherein the relithiated lithium intercalation material is as defined in any one of claims 1 to 8.

12. The production anode / use according to any one of claims 9 to 11, wherein the production anode / use is intended for producing the lithium metal or the alloy thereof, preferably is intended for producing lithium metal, preferably wherein the lithium metal or the alloy thereof is in the form of a film, preferably wherein the lithium metal or the alloy thereof is produced by electrodeposition.

13. Production anode / use according to claim 12, wherein the anode is intended to carry out an electrolysis reaction for producing lithium.

14. The production anode / use according to claim 12 or claim 13, wherein the production anode further comprises a current collector and the relithiated lithium intercalation material is deposited on the current collector.

15. Production of an anode / use according to claim 14, wherein the current collector is a metal foil, preferably made of copper, aluminum, stainless steel, titanium or nickel, or made of a conductive carbon material, or a polymer-based current collector.

16. Production of an anode / use according to claim 14 or claim 15, wherein the current collector is coated with a primer, such as a carbonaceous paint.

17. Production of an anode / use according to any one of claims 14 to 16, wherein the current collector is a metal foil made of stainless steel or aluminum, preferably a current collector comprising a carbon-coated aluminum foil.

18. Production anode / use according to any one of claims 9 to 11, wherein the production anode / use is intended to pre-lithiate an electrode material, preferably to pre-lithiate an anode material, more preferably to pre-lithiate graphite, silicon, silicon oxide (SiO x ), pre-lithiation of silicon-carbon composite materials, carbon nanotubes or their mixtures.

19. The production anode / use according to any one of claims 9 to 18, wherein the production anode is in the form of a membrane.

20. A production electrolytic cell for producing lithium metal or its alloys or for pre-lithiating electrode materials, the production electrolytic cell comprising: Used as relithiated lithium intercalation material to produce anodes, Used as a current collector or said electrode material to produce a cathode, and A generation electrolyte is disposed between the generation cathode and the generation anode, wherein the generation electrolyte comprises a generation lithium salt dissolved in a generation solvent.

21. Use of a production electrolytic cell for producing lithium metal or its alloys or for pre-lithiating an electrode material, wherein the production electrolytic cell comprises: Used as relithiated lithium intercalation material to produce anodes, Used as a current collector or said electrode material to produce a cathode, and A generation electrolyte is disposed between the generation cathode and the generation anode, wherein the generation electrolyte comprises a generation lithium salt dissolved in a generation solvent.

22. A production electrolytic cell / use according to claim 20 or claim 21, wherein the relithiated lithium intercalation material is as defined in any one of claims 1 to 8.

23. The production electrolysis cell / use according to any one of claims 20 to 22, wherein the production anode is as defined in any one of claims 9 to 19.

24. The production electrolytic cell / use according to any one of claims 20 to 23, which is intended for producing the lithium metal or the alloy thereof, preferably is intended for producing lithium metal, preferably wherein the lithium metal or the alloy thereof is in the form of a film, preferably wherein the lithium metal or the alloy thereof is produced by electrodeposition, and wherein the current collector serves as a production cathode.

25. Production electrolysis cell / use according to claim 24, wherein the current collector used as production cathode is in the form of a foil.

26. A production electrolytic cell / use according to claim 24 or claim 25, wherein operating conditions such as agitation and / or temperature control are used to modify the morphology of the produced lithium metal or alloys thereof.

27. The production electrolytic cell / use according to any one of claims 24 to 26, wherein the current collector used as the production cathode is made of one of copper, aluminum, protected aluminum, carbon, stainless steel, titanium, zinc or nickel, or an alloy thereof, or is a current collector based on a metallized polymer or a mixture thereof.

28. The production electrolytic cell / use according to any one of claims 24 to 27, wherein the current collector used as the production cathode is made of protected copper or aluminum.

29. The production electrolysis cell / use according to any one of claims 24 to 28, wherein the current collector used as production cathode is protected by a protective layer.

30. The production electrolysis cell / use according to any one of claims 24 to 28, wherein the current collector used as production cathode is unprotected.

31. The production electrolytic cell / use according to any one of claims 24 to 30, wherein the surface of the current collector used as the production cathode is treated or modified to improve its lithiophilicity.

32. The production electrolysis cell / use according to any one of claims 24 to 31 , wherein the surface of the current collector used as a production cathode is treated or modified to have a 3D structure in order to improve the electrochemical properties of the lithium layer in the battery or to increase its reaction rate, for example, when used to prepare an organic lithium compound.

33. The production electrolytic cell / use according to any one of claims 24 to 32, wherein the production electrolytic cell / use is intended for producing the alloy; preferably, the alloy comprises about 80% w / w or more lithium, more preferably about 85% w / w or more lithium, even more preferably about 90% w / w or more lithium, even more preferably about 95% w / w or more lithium, based on the total weight of the alloy.

34. Production electrolysis cell / use according to claim 33, wherein the production electrolyte further comprises an alloying salt, preferably a salt of one or more of the following elements: sodium, potassium, magnesium, calcium, a transition metal, aluminum, gallium or tin, preferably a salt of aluminum or magnesium.

35. The electrolytic cell / use according to claim 34, wherein the alloying salt is (fluorosulfonyl)(trifluoromethanesulfonyl)imide salt, 2-trifluoromethyl-4,5-dicyanoimidazole (TDI) salt, 4,5-dicyano-1,2,3-triazole (DCTA) salt, bis(pentafluoroethylsulfonyl)imide (BETI) salt, difluorophosphate (DFP), chloride salt, bromide salt, fluoride salt, hexafluoroarsenate (AsF6), fluoroalkyl phosphate salt , tetrakis(trifluoroacetoxy)borate, bis(1,2-benzenediol (2-)-O,O′)borate, difluoro(oxalato)borate, nitrate, trifluoroacetate, hexafluorophosphate, tetrafluoroborate, bis(oxalato)borate (BOB) salt, perchlorate, bis(trifluoromethanesulfonyl)imide (TFSI) salt, bis(fluorosulfonyl)imide (FSI) salt, trifluoromethanesulfonate, or a salt containing an anion having the formula: BF2O4R x - (R x =C 2-4 alkyl).

36. The production electrolytic cell / use according to any one of claims 24 to 32, wherein the production electrolyte is free of alloying salts and the production electrolytic cell / use is intended for the production of lithium metal.

37. The production electrolysis cell / use according to any one of claims 20 to 23, wherein the production electrolysis cell / use is intended for pre-lithiation of an electrode material, preferably for pre-lithiation of an anode material, more preferably for pre-lithiation of graphite, silicon, silicon oxide or a mixture thereof, and wherein the electrode material is used as a production cathode.

38. The production electrolytic cell / use according to any one of claims 20 to 37, wherein the production lithium salt is lithium (fluorosulfonyl) (trifluoromethanesulfonyl) imide, lithium 2-trifluoromethyl-4,5-dicyanoimidazole (LiTDI), lithium 4,5-dicyano-1,2,3-triazole (LiDCTA), lithium bis(pentafluoroethylsulfonyl) imide (LiBETI), lithium difluorophosphate (LiDFP), lithium chloride (LiCl), lithium bromide (LiBr), lithium hexafluoroarsenate (LiAsF6 - ), lithium fluoroalkyl phosphates [such as LiPF3(CF2CF3)3], lithium tetrakis(trifluoroacetoxy)borate (LiB(OCOCF3)4), bis(1,2-benzenedioate ion (2-)-O,O') lithium borate LiB(C6O2)2, lithium difluoro(oxalate ion) borate (LiBF2(C2O4)), having the formula BF2O4R x - (R x =C 2-4 alkyl), LiCF3COO, LiF, LiNO3, LiPF6, LiBF4, LiBOB, LiClO4, LiTFSi, CF3SO3Li, LiFSi, or any combination thereof, preferably LiCF3COO, LiF, LiNO3, LiPF6, LiBF4, LiBOB, LiClO4, LiTFSi, CF3SO3Li, LiFSi, or any combination thereof.

39. The production electrolytic cell / use according to claim 38, wherein the produced lithium salt is a combination of CF3SO3Li and LiFSi.

40. The production electrolysis cell / use according to any one of claims 20 to 39, wherein the production electrolyte further comprises one or more additives, preferably one or more additives that change the morphology and / or properties of the lithium metal or its alloys, one or more additives that influence phase nucleation energy, one or more additives that influence the deposition potential of the lithium or its alloys and / or one or more additives that influence the electrodeposition efficiency of lithium; more preferably, the additives are the following: Cyclic unsaturated carbonates, such as vinylene carbonate (VC), Halogenated cyclic carbonates, such as fluoroethylene carbonate (FEC), nitrates, a lithium polymerizing agent comprising a saturated or unsaturated hydrocarbon chain, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), lithium passivating compounds, and / or Basic salts of organic acids, such as lithium difluoro(oxalate)borate (LiDFOB) or lithium oxalate.

41. The production electrolysis cell / use according to any one of claims 20 to 40, wherein the production solvent is an organic carbonate, an organic ester, an organic ether, an ionic liquid or any combination thereof.

42. The production electrolysis cell / use of claim 41, wherein the production solvent is ethylene carbonate (EC), propylene carbonate (PC), fluoroethylene carbonate (FEC), gamma-butyrolactone (gBL), ethyl propionate, diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), dimethoxyethane (DME), fluoroether, tetrafluoroethyltetrafluoropropyl ether (TTE), tetraethylene glycol dimethyl ether (TEGDME), or any combination thereof.

43. The production electrolysis cell / use according to claim 42, wherein the production solvent is a combination of EC and DEC.

44. The production electrolysis cell / use according to any one of claims 20 to 43, wherein the production electrolysis cell is free of a membrane separating the production anode from the production cathode.

45. The production electrolysis cell / use according to claim 44, wherein the production electrolysis cell is in a roll-to-roll configuration.

46. ​​Production cell / use according to claim 44 or claim 45, wherein the production cell further comprises one or more calendering devices, such as pairs of calendering rollers, at regular intervals.

47. A method for producing lithium metal or its alloys or pre-lithiating an electrode material, the method comprising: a) providing a relithiated lithium intercalation material, and b) carrying out an electrolytic reaction for producing lithium in a production electrolytic cell, wherein the production electrolytic cell comprises: as the relithiated lithium intercalation material producing the anode, as a current collector or said electrode material for producing a cathode, and a generation electrolyte disposed between the generation cathode and the generation anode, wherein the generation electrolyte comprises a generation lithium salt dissolved in a generation solvent, thereby enabling the electrodeposition of lithium metal or its alloys on the current collector used to produce the cathode, or introducing lithium into the electrode material, thereby producing a pre-lithiated electrode, and This enables the production of partially or completely delithiated lithium intercalation materials.

48. The method of claim 47, wherein the relithiated lithium intercalation material is as defined in any one of claims 1 to 8.

49. A method according to claim 47 or claim 48, wherein the production anode is as defined in any one of claims 9 to 19.

50. A method according to any one of claims 47 to 49, wherein the production electrolytic cell is as defined in any one of claims 20 to 46.

51. according to the method described in any one of claim 47 to 50, wherein said electrolysis reaction for producing lithium is carried out by regulating the cell potential between said producing anode and said producing cathode or between said cathode and a reference electrode.

52. The method of any one of claims 47 to 50, wherein the electrolysis reaction for producing lithium is performed by adjusting the cell current.

53. The method of claim 52, wherein the electrolysis reaction for producing lithium is carried out in a direct mode, a pulse mode, whether a simple (unidirectional) mode or a reverse mode, in a current-controlled mode.

54. The method of claim 52 or claim 53, wherein the electrolysis reaction for producing lithium is carried out at a fixed frequency or a variable frequency in a regulated current mode.

55. The method of any one of claims 47 to 54, wherein step a) is performed in a roll-to-roll configuration.

56. A method according to any one of claims 47 to 55, wherein step b) is performed in a roll-to-roll configuration.

57. The method according to any one of claims 47 to 56, wherein the partially or fully delithiated lithium intercalation material is lithium phosphate or partially or fully delithiated lithium oxide, preferably partially or fully delithiated Li w FePO4、Li w Mn2O4、Li 4+ z Ti5O 12 or NMC(Li w Ni 1-x-y Mn x Co y M z O2).

58. The method of claim 57, wherein the partially or fully delithiated lithium intercalation material is a partially or fully delithiated Li w FePO4.

59. The method of any one of claims 47 to 58, wherein the relithiated lithium intercalation material is washed, preferably washed and dried, prior to use in step b).

60. The method according to any one of claims 47 to 59, wherein step a) comprises: a′) providing a partially or fully delithiated lithium intercalation material, and a″) relithiating the partially or fully delithiated lithium intercalation material, thereby enabling the production of a relithiated lithium intercalation material.

61. The method according to claim 60, further comprising step c) of repeating steps a) and b) one or more times, using the partially or fully delithiated lithium intercalation material produced in step b) in steps a') and a").

62. A method according to claim 60 or claim 61, wherein the partially or fully delithiated lithium intercalation material supplied in step a') is the partially or fully delithiated lithium intercalation material produced in step b).

63. The method of any one of claims 47 to 60, wherein the partially or fully delithiated lithium intercalation material is obtained from recycled used batteries.

64. The method of any one of claims 47 to 63, wherein step a") comprises performing an electrolytic relithiation reaction in an electrolytic relithiation cell, wherein the electrolytic relithiation cell comprises: as said partially or fully delithiated intercalation material for a relithiated cathode, Relithiated anode, and a relithiated electrolyte disposed between the relithiated cathode and the relithiated anode, wherein the relithiated electrolyte comprises a relithiated lithium salt dissolved in a relithiated solvent, This enables the partially or fully delithiated intercalation material to be relithiated and produces the relithiated lithium intercalation material.

65. The method of claim 64, wherein the relithiation solvent is water.

66. A method according to claim 64 or claim 65, wherein the relithiated anode is made of a material that is compatible with the anode reaction occurring at the relithiated anode, preferably with the oxygen evolution reaction.

67. The method of any one of claims 64 to 66, wherein the relithiation anode is made of lead, platinum, titanium, another inert metal, or one of their alloys, or graphite.

68. The method of any one of claims 64 to 67, wherein the relithiated anode is a dimensionally stable anode.

69. The method of any one of claims 64 to 68, wherein the relithiation electrolyte further comprises one or more additives; preferably one or more additives that improve the conductive properties of the relithiation electrolyte; more preferably comprises a salt of an alkali cation other than lithium or an alkaline earth cation (preferably potassium or magnesium) and an anion compatible with the electrolytic relithiation reaction (preferably sulfate or bicarbonate).

70. The method of any one of claims 64 to 69, wherein the relithiation salt is Li2CO3, LiHCO3, LiOH, LiNO3, LiOH, Li2SO4, LiCH3COO, LiFSI, LiTFSI or Li2C2O4 or a mixture thereof, preferably the relithiation salt is LiHCO3, Li2SO4 or a mixture thereof, preferably the relithiation salt is Li2SO4.

71. The method of any one of claims 64 to 70, wherein the relithiation salt is an inexpensive lithium salt.

72. The method of any one of claims 64 to 71, wherein the relithiation solvent is water and the relithiation salt is a water-soluble relithiation salt.

73. The method of any one of claims 64 to 72, wherein the relithiation salt is a water-soluble relithiation salt having a water solubility greater than that of LiHCO3.

74. The method of claim 73, wherein the water-soluble relithiation salt having a water solubility greater than that of LiHCO3 is LiNO3, Li2SO4, or LiCH3COO.

75. The method of any one of claims 64 to 74, further comprising the step of producing the relithiation salt in the electrolytic relithiation cell.

76. The method of claim 75, comprising adding a lithium precursor and a reagent to the electrolytic relithiation cell, and reacting the lithium precursor with the reagent to form the relithiation salt.

77. The method of claim 76, wherein the lithium precursor and the reagent are added to a salt formation compartment of the electrolytic relithiation cell, the salt formation compartment being in fluid communication with a main compartment of the electrolytic relithiation cell; the main compartment comprising the relithiation cathode and the relithiation anode.

78. The method of any one of claims 64 to 74, wherein the relithiation salt is prepared prior to addition to the electrolytic relithiation cell.

79. The method of claim 78, further comprising reacting a lithium precursor and a reagent in a reactor separate from the electrolytic relithiation cell to obtain the relithiation salt, and then adding the relithiation salt to the electrolytic relithiation cell.

80. The method according to any one of claims 76, 77 and 79, wherein the lithium precursor is Li2CO3, LiOH or a mixture thereof, preferably Li2CO3.

81. The method of any one of claims 76, 77, 79 or 80, wherein the reagent is CO2, H2SO4, nitric acid, acetic acid, oxalic acid or an acid form of a sulfonyl imide salt or a mixture thereof, preferably CO2 or H2SO4 or a mixture thereof.

82. The method of claim 81, wherein the reagent is CO2.

83. The method of claim 81, wherein the reagent is H2SO4.

84. The method of any one of claims 64 to 83, wherein the electrolytic relithiation reaction is performed by adjusting the cell potential between the relithiated anode and the relithiated cathode or between the relithiated cathode and a reference electrode.

85. The method of any one of claims 64 to 83, wherein the electrolytic relithiation reaction is performed by adjusting the cell current.

86. The method of claim 85, wherein the electrolysis reaction can be carried out in direct mode, pulse mode, whether simple (unidirectional) mode or reverse mode, in current controlled mode.

87. The method of claim 85 or claim 86, wherein the electrolysis reaction can be carried out at a fixed frequency or a variable frequency in a current controlled mode.

88. The method of any one of claims 47 to 63, wherein step a″) comprises (i) adding the partially or fully delithiated intercalation material to a solution comprising a reducing agent and a relithiating salt in a solvent; thereby enabling relithiation of the partially or fully delithiated intercalation material and producing the relithiated lithium intercalation material.

89. The method of claim 88, further comprising (ii) separating the relithiated lithium intercalation material from the solution; and (iii) electrochemically treating the solution separated in step (ii) to regenerate the reducing agent.

90. The method of claim 88 or claim 89, wherein the relithiation salt is as described in any one of claims 70 to 74.

91. The method of any one of claims 88 to 90, wherein the reducing agent is the reducing member of a redox pair, the reducing member having a redox potential lower than the redox potential of the partially or fully delithiated intercalation material.

92. The method of claim 91, wherein the redox couple comprises an Fe(III) / Fe(II) complex.

93. The method of claim 92, wherein the redox couple is [Fe(CN)6] 3- / Fe(CN)6] 4- 、[Fe(nta)] / [Fe(nta)] - 、[Fe(tdpa)] 2- / Fe(tdpa)] 3- , [Fe(edta)] - / [Fe(edta)] 2- , [Fe(citrate)] / [Fe(citrate)] - , [Fe(III)-TEA] / [Fe(II)-TEA] or [Fe(oxalate)] + / [Fe(oxalate)].

94. The method of any one of claims 88 to 93, wherein step (i) further comprises deoxygenating the solution.

95. The method of any one of claims 88 to 94, wherein steps (i) and / or (iii) are performed in the absence of oxygen.

96. The method of any one of claims 88 to 95, further comprising adjusting the pH of the solution.

97. The method of any one of claims 88 to 96, wherein the solvent is an aqueous solvent.

98. The method of any one of claims 88 to 97, wherein step (iii) is performed in an electrolytic cell by passing electricity between at least one cathode and at least one anode.

99. The method of claim 98, wherein the electrolytic cell comprises at least one ionic or non-ionic membrane installed between the anode and the cathode to protect the regenerated reducing agent.

100. The method of claim 98 or claim 99, wherein the electrolytic cell further comprises a system for maintaining a deoxygenated solution.

101. according to the method described in any one of claim 98 to 100, wherein step (iii) is carried out by adjusting the cell potential between the anode and the cathode or between the cathode and a reference electrode.

102. The method of any one of claims 98 to 100, wherein step (iii) is performed by adjusting the cell current.

103. The method of claim 102, wherein the relithiation reaction is carried out in direct mode, pulse mode, whether simple (unidirectional) mode or reverse mode, under regulated current mode.

104. The method of claim 102 or claim 103, wherein the relithiation reaction is performed at a fixed frequency or a variable frequency in a regulated current mode.

105. The method according to any one of claims 47 to 104, further comprising washing and drying the current collector with the lithium metal or the alloy thereof, or the pre-lithiated electrode produced in step b).

106. A method according to any one of embodiments 47 to 105, which further comprises using the collector having the lithium metal or the alloy thereof, or the pre-lithiated electrode as a negative electrode in a primary or secondary lithium battery, preferably a lithium-ion battery or an all-solid-state battery, as a source of lithium metal or the alloy thereof for pre-lithiating electrode materials, or as a source of lithium metal or the alloy thereof for manufacturing an energy storage system.

107. The method of any one of claims 47 to 106, further comprising rolling the current collector having the lithium metal or the alloy thereof to change the morphology, density or film thickness of the lithium metal or the alloy thereof.

108. The method of any one of claims 47 to 107, further comprising processing the current collector having the lithium metal or the alloy thereof to have a 3D structure.

109. The method of any one of claims 47 to 108, further comprising treating the current collector having the lithium metal or the alloy thereof to improve its electrochemical performance in a battery.

110. The method of any one of claims 47 to 105, further comprising using the current collector having the lithium metal or the alloy thereof as a lithium source to produce an organolithium compound.

111. The method of claim 110, wherein the lithium metal or the alloy thereof is reacted with a reagent such as an alkyl halide to produce the organolithium compound.

112. The method according to claim 110, further comprising transferring the current collector having the lithium metal or the alloy thereof produced in step b) to a separate reactor, preferably in roll-to-roll mode, and reacting the lithium metal or the alloy thereof with a reactant in the separate reactor to produce the organic lithium compound.

113. The method according to any one of claims 47 to 112, which is intended to prelithiate an electrode material, preferably to prelithiate an anode material, more preferably to prelithiate graphite, silicon, silicon oxide (SiO x ), silicon-carbon composite materials, carbon nanotubes or mixtures thereof are pre-lithiated, and wherein the electrode material is used to produce a cathode.

114. A method according to any one of claims 47 to 112, which is intended to produce said lithium metal or said alloy thereof, preferably intended to produce said lithium metal, preferably wherein said lithium metal or said alloy thereof is produced by electrodeposition, and wherein said current collector is used to produce a cathode.

115. The method of claim 114, wherein the lithium metal or the alloy thereof is electrolytically deposited on the current collector in the form of a film, preferably a high purity film.

116. A lithium electrode comprising a current collector comprising lithium metal or an alloy thereof as produced by the method of any one of claims 47 to 115.

117. A lithium battery comprising the lithium electrode according to claim 116, preferably wherein the battery is a lithium ion battery or an all-solid-state battery.

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