Method for producing lithium metal or its alloys or for prelithiating electrode materials

Abstract

The present invention relates to a relithiated lithium insertion material for producing lithium metal or for prelithiating electrode materials, as well as an anode and a manufacturing electrolytic cell comprising the material. The present invention also relates to a method for producing lithium metal and for prelithiating electrode materials, which method comprises conducting an electrolytic reaction to produce lithium in an electrolytic cell comprising the relithiated lithium insertion material as the anode, a current collector as the cathode, and an electrolyte comprising a lithium salt.

Description

[Technical Field]

[0001] The present invention relates to methods for producing lithium metal or alloys thereof or for prelithiating electrode materials. More particularly, the present invention relates to methods for producing lithium metal or alloys thereof in some cases and for prelithiating electrode materials in other cases from relithiated lithium insertion materials. [Background technology]

[0002] Lithium metal is conventionally produced by electrolysis of LiCl in a molten salt medium at very high temperatures (typically 400-450°C). The electrolyte consists of a mixture of LiCl and KCl, thereby forming a eutectic mixture 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 evolved at the anode during electrolysis and has a current density of several thousand A / m 2 Current densities of up to 10 ...

[0003] To reduce the electrolysis temperature and avoid handling liquid lithium metal, it has been proposed to carry out the electrodeposition of lithium in room temperature ionic liquids (RTILs). However, the proposed approach leaves open the question of whether an anodic reaction can occur that does not lead to degradation of the electrolysis medium.

[0004] The use of lithium metal as an anode material has been proposed with the aim of avoiding electrolyte degradation during the anodic reaction during lithium metal electrodeposition. This approach has been applied to both the production of lithium films on current collectors and the prelithiation of anode materials (such as graphite and silicon). However, this approach, which relies on the oxidation of lithium as the compatible anodic reaction, involves the use of lithium metal produced by conventional high-temperature methods using LiCl as the starting material.

[0005] Bodoin et al. (US 2022 / 0367874 A1) and Kang et al. (2021 / 0381115 A1) proposed the use of an electrolysis cell equipped 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 containing another lithium salt. This method has several advantages: anodic reactions incompatible with the electrolysis medium (in this case, the anodic reaction is the release of oxygen in the aqueous medium) are avoided; electrolysis is performed at low temperatures; and the raw material for lithium metal production can be any lithium salt, such as lithium carbonate. Furthermore, the proposed approach also has several important drawbacks, including the use of an expensive and fragile ceramic membrane; leakage of water molecules through the ceramic membrane into the organic electrolyte; and the resulting contamination of lithium metal with LiOH.

[0006] On a separate topic, next-generation energy storage technologies require advanced active electrode materials with improved gravimetric and volumetric capacities to enhance gravimetric and volumetric energy densities. However, most of these materials suffer from significant loss of active lithium during the first cycle, due to factors such as the formation of a solid electrolyte interface (SEI), which has hindered their widespread commercial use to date. Indeed, when a battery is first charged, a certain amount of active lithium is lost, resulting in a decrease in the remaining active lithium content. Generally, the loss of active lithium permanently reduces the available energy due to lithium consumption by the electrode material. Prelithiation is considered a very interesting technique to compensate for the loss of active lithium and consequently increase the actual energy density. Prelithiation involves adding / doping lithium to battery electrodes before the operation of the battery cell. Prelithiation can effectively compensate for the lithium loss during the first cycle and improve the initial coulombic efficiency. This is a general method that can be applied to all types of electrode materials and can improve battery performance. Various prelithiation techniques have been evaluated, including electrochemical and chemical prelithiation, prelithiation using additives, and even prelithiation by direct contact with lithium metal.

[0007] In the electrochemical prelithiation method, the lithium source consists of a lithium metal electrode bonded to a lithium insertion material. When a current is applied, the lithium metal oxidizes and migrates to the opposite electrode, where it is inserted into the lithium insertion material. Such a method has been applied to the prelithiation of silicone intercalation materials by Park et al. (WO 2019 / 113534 A1). In this patent application, the use of a lithium metal counter electrode increases costs, and the aforementioned problems associated with the use of highly reactive lithium metal persist. To avoid the problems associated with using lithium metal as the lithium source for prelithiation, Grant et al. (US9598789B2) developed an anode prelithiation method 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 with an inert metal foil where anode electrolyte degradation reactions, such as chlorine evolution, are expected. Such systems are prone to electrolyte salt degradation, high power consumption, and limited current density. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] US Patent Application Publication No. 2022 / 0367874A1 [Patent Document 2] U.S. Patent Application Publication No. 2021 / 0381115A1 [Patent Document 3] International Publication No. 2019 / 113534A1 [Patent Document 4] U.S. Patent No. 9,598,789 B2 Summary of the Invention

[0009] According to the present invention, there is provided: 1. Relithiated lithium insertion materials to produce lithium metal or its alloys or to prelithiate electrode materials. 2. Use of the relithiated lithium insertion material to produce lithium metal or its alloys or to prelithiate electrode materials. 3. The material / use of embodiment 1 or embodiment 2 for producing lithium metal or an alloy thereof, preferably for producing lithium metal, preferably the lithium metal or an alloy thereof in the form of a film, preferably the lithium metal or an alloy thereof is produced by electrodeposition. 4. For pre-lithiation of electrode materials, preferably for pre-lithiation of anode materials, more preferably for pre-lithiation of graphite, silicon, silicon oxide (SiO x ), silicon-carbon composites, carbon nanotubes, or mixtures thereof, the material / use according to Embodiment 1 or Embodiment 2. 5. The re-lithiated lithium insertion material is lithium phosphate or lithium oxide, preferably, ·Li w FePO4, Li w Fe 1-x Mn x PO4, Li w Mn2O4, Li w Mn 1.5 Ni 0.5 O4, Li 4+z Ti5O 12 , or NMC, in the formula Li w FePO4, w ≤ 1.1, preferably w is 1, · In the formula Li w Fe 1-x Mn x PO4, w ≤ 1.1, preferably w is 1, x is in the range of 0 < x ≤ 1, preferably in the range of 0.2 < x ≤ 0.4, · In the formula Li w Mn2O4, w ≤ 1.1, preferably w is 1, · In the formula Li w Mn 1.5 Ni 0.5 O4, w ≤ 1.1, preferably w is 1, · In the formula Li 4+z Ti5O 12 , z is in the range of 0 < z ≤ 3, · NMC is Li w Ni 1-x-y Mn x Co y5. The material / use of any one of embodiments 1 to 4, wherein w≦1.3, preferably w is 1, x is in the range of 0≦x≦1, y is in the range of 0≦y≦1, z is in the range of 0≦z≦1, and M is aluminum, magnesium, titanium, niobium, zirconium, tungsten, molybdenum, yttrium, lanthanum, tantalum, or a mixture thereof. 6. Relithiated lithium insertion materials are Li w 6. The material / use of embodiment 5, wherein the material / use is FePO4. 7. The material / use of any one of embodiments 1-6, wherein the relithiated lithium insertion material is obtained from a used electrode and then relithiated, or the relithiated lithium insertion material is used to make lithium metal or an alloy thereof, or to prelithiate an electrode material, and then relithiated. 8. The material / use of any one of embodiments 1 to 7, wherein the relithiated lithium insertion material has recovered at least 50%, preferably at least 75%, more preferably at least 85%, even more preferably at least 95%, and most preferably at least 99% of the previously deintercalated lithium ions. 9. A manufacturing anode for producing lithium metal or an alloy thereof or for prelithiating an electrode material, the manufacturing anode comprising a relithiated lithium insertion material. 10. Use of a manufacturing anode comprising a relithiated lithium insertion material to produce lithium metal or an alloy thereof or to prelithiate an electrode material. 11. The anode for producing / use of embodiment 9 or embodiment 10, wherein the relithiated lithium insertion material is as defined in any one of embodiments 1 to 8. 12. The manufacturing anode / use of any one of embodiments 9 to 11, for the production of lithium metal or an alloy thereof, preferably for the production of lithium metal, preferably the lithium metal or an alloy thereof is in the form of a film, preferably the lithium metal or an alloy thereof is produced by electrodeposition. 13. The manufacturing anode / use according to embodiment 12, wherein the anode is intended for an electrolytic reaction to produce lithium. 14. The manufacturing anode / use of embodiment 12 or embodiment 13, wherein the manufacturing anode further comprises a current collector, and the relithiated lithium insertion material is deposited on the current collector. 15. The manufacturing anode / use according to embodiment 14, wherein the current collector is a metal foil, preferably a foil made of copper, aluminum, stainless steel, titanium or nickel, or is made of a conductive carbon material, or is a polymer-based current collector. 16. The manufacturing anode / use of embodiment 14 or embodiment 15, wherein the current collector is coated with a primer, such as a carbon-containing paint. 17. The manufacturing anode / use of any one of embodiments 14-16, wherein the current collector is a current collector comprising a metal foil made of stainless steel or aluminum, preferably an aluminum foil coated with carbon. 18. For prelithiating electrode materials, preferably for prelithiating anode materials, more preferably graphite, silicon, silicon oxide (SiO x 12. The manufacturing anode / use of any one of embodiments 9 to 11 for prelithiating silicon-carbon composites, carbon nanotubes, or mixtures thereof. 19. The manufacturing anode / use of any one of embodiments 9 to 18, wherein the manufacturing anode is in the form of a film. 20. A manufacturing electrolytic cell for producing lithium metal or its alloys or for prelithiating electrode materials, the manufacturing electrolytic cell comprising: a relithiated lithium insertion material used as a fabrication anode; a current collector or electrode material used as a manufacturing cathode; A manufacturing electrolytic cell comprising a manufacturing electrolyte between a manufacturing cathode and a manufacturing anode, the manufacturing electrolyte comprising a manufacturing lithium salt dissolved in a manufacturing solvent. 21. Use of a production electrolytic cell for producing lithium metal or an alloy thereof or for prelithiating an electrode material, the production electrolytic cell comprising: a relithiated lithium insertion material used as a fabrication anode; a current collector or electrode material used as a manufacturing cathode; Use of a manufacturing electrolytic cell comprising a manufacturing electrolyte between a manufacturing cathode and a manufacturing anode, the manufacturing electrolyte comprising a manufacturing lithium salt dissolved in a manufacturing solvent. 22. The manufacturing electrolytic cell / use of embodiment 20 or embodiment 21, wherein the relithiated lithium insertion material is as defined in any one of embodiments 1-8. 23. The manufacturing electrolytic cell / use of any one of embodiments 20-22, wherein the manufacturing anode is as defined in any one of embodiments 9-19. 24. The manufacturing electrolytic cell / use of any one of embodiments 20-23, for the production of lithium metal or an alloy thereof, preferably for the production of lithium metal, preferably the lithium metal or an alloy thereof is in the form of a film, preferably the lithium metal or an alloy thereof is produced by electrodeposition, and the current collector is used as a manufacturing cathode. 25. The manufacturing electrolysis cell / use of embodiment 24, wherein the current collector used as the manufacturing cathode is in the form of a foil. 26. The process electrolytic cell / use of embodiment 24 or embodiment 25, wherein operating conditions such as stirring and / or temperature control are used to modify the morphology of the produced lithium metal or alloy thereof. 27. The manufacturing electrolysis cell / use of any one of embodiments 24-26, wherein the current collector used as the manufacturing cathode is made from copper, aluminum, protected aluminum, carbon, stainless steel, titanium, zinc, nickel, or one of their alloys, or is a metallized polymer-based current collector, or a mixture thereof. 28. The manufacturing electrolysis cell / use of any one of embodiments 24-27, wherein the current collector used as the manufacturing cathode is made from protected copper or aluminum. 29. The production electrolysis cell / use of any one of embodiments 24-28, wherein the current collector used as the production cathode is protected by a protective layer. 30. The production electrolysis cell / use of any one of embodiments 24-28, wherein the current collector used as the production cathode is unprotected. 31. The manufacturing electrolytic cell / use of any one of embodiments 24-30, wherein the surface of the current collector used as the manufacturing cathode is treated or modified to improve its lithophilicity. 32. The manufacturing electrolysis cell / use of any one of embodiments 24-31, wherein the surface of the current collector used as the manufacturing cathode is treated or modified to have a 3D structure, for example to improve the electrochemical performance of the lithium layer in the battery when used in the preparation of organolithium compounds, or to increase its reaction rate. 33. The manufacturing electrolytic cell / use of any one of embodiments 24 to 32, intended for producing the alloy, preferably comprising at least about 80% w / w lithium, more preferably at least about 85% w / w lithium, even more preferably at least about 90% w / w lithium, and even more preferably at least about 95% w / w lithium, based on the total weight of the alloy. 34. The manufacturing electrolysis cell / use of embodiment 33, wherein the manufacturing electrolyte further comprises an alloy salt, the alloy salt being preferably a salt of one or more elements of sodium, potassium, magnesium, calcium, a transition metal, aluminum, gallium, or tin, more preferably an aluminum or magnesium salt. 35. Alloy salts include (fluorosulfonyl)(trifluoromethanesulfonyl)imide salts, 2-trifluoromethyl-4,5-dicyanoimidazolate (TDI) salts, 4,5-dicyano-1,2,3-triazolate (DCTA) salts, bis(pentafluoroethylsulfonyl)imide (BETI) salts, difluorophosphate (DFP), chloride salts, bromide salts, fluoride salts, hexafluoroarsenate (AsF6), fluoroalkylphosphate salts, and tetrakis. Bis(trifluoroacetoxy)borate, bis(1,2-benzenediolato(2-)-O,O')borate, difluoro(oxalato)borate, nitrate, trifluoroacetate, hexafluorophosphate, tetrafluoroborate, bis(oxalato)borate (BOB), perchlorate, bis(trifluoromethanesulfonyl)imide (TFSI) salt, bis(fluorosulfonyl)imide (FSI) salt, triflate salt, or a salt of the formula BF2O4R x - (R x =C 2-4 35. The manufacturing electrolysis cell / use of embodiment 34, wherein the salt has an anion having a hydroxyl group (alkyl). 36. The manufacturing electrolytic cell / use of any one of embodiments 24-32, wherein the manufacturing electrolyte does not contain alloy salts and the manufacturing electrolytic cell / use is intended to produce lithium metal. 37. The manufacturing electrolytic cell / use of any one of embodiments 20-23, wherein the electrode material is intended to be prelithiated, preferably an anode material, more preferably graphite, silicon, silicon oxide, or a mixture thereof, and the electrode material is used as a manufacturing cathode. 38. Manufacturing lithium salts include lithium (fluorosulfonyl)(trifluoromethanesulfonyl)imide, lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium difluorophosphate (LiDFP), lithium chloride (LiCl), lithium bromide (LiBr), and lithium hexafluoroarsenate (LiAsF6- ), lithium fluoroalkylphosphate [such as LiPF3(CF2CF3)3], lithium tetrakis(trifluoroacetoxy)borate (LiB(OCOCF3)4), lithium bis(1,2-benzenediolato(2-)-O,O')borate (LiB(C6O2)2), lithium difluoro(oxalato)borate (LiBF2(C2O4)), formula BF2O4R x - , LiCF3COO, LiF, LiNO3, LiPF6, LiBF4, LiBOB, LiClO4, LiTFSi, CF3SO3Li, LiFSi or any combination thereof, preferably compounds having the formula LiCF3COO, LiF, LiNO3, LiPF6, LiBF4, LiBOB, LiClO4, LiTFSi, CF3SO3Li, LiFSi or any combination thereof, and x - In R x =C 2-4 38. The manufacturing electrolysis cell / use of any one of embodiments 20 to 37, wherein the alkyl is alkyl. 39. The manufacturing electrolytic cell / use of embodiment 38, wherein the manufacturing lithium salt is a combination of CF3SO3Li and LiFSi. 40. The manufacturing electrolyte further comprises one or more additives, preferably one or more additives that modify the morphology and / or properties of lithium metal or its alloys, one or more additives that affect the phase nucleation energy, one or more additives that affect the deposition potential of lithium or its alloys, and / or one or more additives that affect the electrodeposition efficiency of lithium, more preferably the additive(s) are / are: Cyclic unsaturated carbonates such as vinylene carbonate (VC), Halogenated cyclic carbonates such as fluoroethylene carbonate (FEC), nitrate, Lithium polymerization agents containing saturated or unsaturated hydrocarbon chains, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU); lithium passivation compounds, and / or 40. The manufacturing electrolysis cell / use of any one of embodiments 20-39, wherein the alkali salt of an organic acid is lithium difluoro(oxalato)borate (LiDFOB) or lithium oxalate. 41. The manufacturing electrolysis cell / use of any one of embodiments 20-40, wherein the manufacturing solvent is an organic carbonate, an organic ester, an organic ether, an ionic liquid, or any combination thereof. 42. The manufacturing electrolytic cell / use of embodiment 41, wherein the manufacturing 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), a fluoroether, tetrafluoroethyl tetrafluoropropyl ether (TTE), tetraethylene glycol dimethyl ether (TEGDME), or any combination thereof. 43. The manufacturing electrolytic cell / use of embodiment 42, wherein the manufacturing solvent is a combination of EC and DEC. 44. The production electrolysis cell / use of any one of embodiments 20-43, wherein the production electrolysis cell does not include a membrane separating the production anode from the production cathode. 45. The manufacturing electrolytic cell / use of embodiment 44, wherein the manufacturing electrolytic cell is a roll-to-roll construction. 46. ​​The manufacturing electrolytic cell / use of embodiment 44 or embodiment 45, wherein the manufacturing electrolytic cell further comprises one or more calendering devices, for example pairs of spaced calender rolls. 47. A method for producing lithium metal or an alloy thereof or for prelithiating an electrode material, said method comprising: a) providing a relithiated lithium insertion material; b) conducting an electrolytic reaction to produce lithium in a production electrolytic cell, the production electrolytic cell comprising: the relithiated lithium insertion material as a fabrication anode; a current collector or the electrode material as a manufacturing cathode; a production electrolyte between the production cathode and the production anode, the production electrolyte including a production lithium salt dissolved in a production solvent; thereby allowing the electrodeposition of lithium metal or an alloy thereof onto a current collector to be used as a production cathode, or to introduce lithium into an electrode material to produce a prelithiated electrode; thereby enabling the production of a partially or fully delithiated lithium insertion material. 48. The method of embodiment 47, wherein the relithiated lithium insertion material is as defined in any one of embodiments 1-8. 49. The method of embodiment 47 or embodiment 48, wherein the fabricating anode is as defined in any one of embodiments 9 to 19. 50. The method of any one of embodiments 47-49, wherein the production electrolytic cell is as defined in any one of embodiments 20-46. 51. The method of any one of embodiments 47-50, wherein the electrolytic reaction for producing lithium is carried out by adjusting the cell potential between the production anode and the production cathode, or between the cathode and the reference electrode. 52. The method of any one of embodiments 47-50, wherein the electrolysis reaction for producing lithium is carried out by adjusting the cell current. 53. The method according to embodiment 52, wherein the electrolysis reaction for producing lithium in current-controlled mode is carried out in direct current mode, pulse mode, whether in simple (unidirectional) mode or in reverse mode. 54. The method according to embodiment 52 or embodiment 53, wherein the electrolysis reaction for producing lithium in regulated current mode is carried out at a fixed frequency or at a variable frequency. 55. The method of any one of embodiments 47-54, wherein step a) is performed in a roll-to-roll configuration. 56. The method of any one of embodiments 47-55, wherein step b) is performed in a roll-to-roll configuration. 57. The partially or fully delithiated lithium insertion 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 57. The method of any one of embodiments 47-56, wherein O2). 58. Partially or fully delithiated lithium insertion material is a partially or fully delithiated Li w 58. The method of embodiment 57, wherein the FePO4. 59. The method of any one of embodiments 47-58, wherein the relithiated lithium insertion material is washed, preferably washed and dried, before being used in step b). 60. Step a) is a') providing a partially or fully delithiated lithium insertion material; a'') relithiating the partially or fully delithiated lithium insertion material to allow for the production of a relithiated lithium insertion material. 61. The method of embodiment 60, further comprising step c) of repeating steps a) and b) one or more times using the partially or fully delithiated lithium insertion material produced in step b) in step a′) and step a″). 62. The method of embodiment 60 or 61, wherein the partially or fully delithiated lithium insertion material provided in step a') is the partially or fully delithiated lithium insertion material produced in step b). 63. The method of any one of embodiments 47-60, wherein the partially or fully delithiated lithium insertion material is obtained from recycled spent batteries. 64. Step a″) comprises conducting an electrolytic relithiation reaction in an electrolytic relithiation cell, the electrolytic relithiation cell comprising: a partially or fully delithiated intercalation material as a relithiated cathode; a relithiated anode; and a relithiated electrolyte between the relithiated cathode and the relithiated anode, the relithiated electrolyte comprising a relithiated lithium salt dissolved in a relithiated solvent; 64. The method of any one of embodiments 47 to 63, thereby enabling relithiation of a partially or fully delithiated insertion material and production of a relithiated lithium insertion material. 65. The method of embodiment 64, wherein the relithiation solvent is water. 66. The method of embodiment 64 or embodiment 65, wherein the relithiated anode is made of a material compatible with the anode reaction occurring in the relithiated anode, preferably a material compatible with the oxygen-releasing reaction. 67. The method of any one of embodiments 64-66, wherein the relithiated anode is made of lead, platinum, titanium, another inert metal, or one of their alloys, or graphite. 68. The method of any one of embodiments 64-67, wherein the relithiated anode is a dimensionally stable anode. 69. The method of any one of embodiments 64-68, wherein the relithiated electrolyte further comprises one or more additives, preferably one or more additives that improve the conductivity of the relithiated electrolyte, more preferably a salt comprising an alkali or alkaline earth cation other than lithium (preferably potassium or magnesium) and an anion compatible with the electrolytic relithiation reaction (preferably sulfate or bicarbonate). 70. The method of any one of embodiments 64-69, wherein the relithiated salt is Li2CO3, LiHCO3, LiOH, LiNO3, LiOH, Li2SO4, LiCH3COO, LiFSI, LiTFSI, Li2C2O4, or a mixture thereof, preferably the relithiated salt is LiHCO3, Li2SO4, or a mixture thereof, more preferably the relithiated salt is Li2SO4. 71. The method of any one of embodiments 64-70, wherein the relithiated salt is an inexpensive lithium salt. 72. The method of any one of embodiments 64-71, wherein the relithiation solvent is water and the relithiation salt is a water-soluble relithiation salt. 73. The method of any one of embodiments 64-72, wherein the relithiated salt is a water-soluble relithiated salt having a water solubility greater than that of LiHCO3. 74. The method of embodiment 73, wherein the water-soluble relithiated salt having a water solubility greater than that of LiHCO3 is LiNO3, Li2SO4, or LiCH3COO. 75. The method of any one of embodiments 64-74, further comprising producing a relithiated salt in an electrolytic relithiation cell. 76. The method of embodiment 75, comprising adding a lithium precursor and a reagent to an electrolytic relithiation cell to react the lithium precursor with the reagent to form a relithiated salt. 77. The method of embodiment 76, wherein the lithium precursor and reagent are added to a salt-forming compartment of the electrolytic relithiation cell that is in fluid communication with a main compartment of the electrolytic relithiation cell, the main compartment comprising a relithiated cathode and a relithiated anode. 78. The method of any one of embodiments 64-74, wherein the relithiation salt is prepared before being added to the electrolytic relithiation cell. 79. The method of embodiment 78, further comprising reacting a lithium precursor with a reagent in a reactor separate from the electrolytic relithiation cell to obtain a relithiated salt, and then adding the relithiated salt to the electrolytic relithiation cell. 80. The method of any one of embodiments 76, 77, and 79, wherein the lithium precursor is Li2CO3, LiOH, or a mixture thereof, preferably Li2CO3. 81. The method of any one of embodiments 76, 77, 79 and 80, wherein the reagent is CO2, H2SO4, nitric acid, acetic acid, oxalic acid, or the acid form of a sulfonylimide salt, or a mixture thereof, preferably CO2 or H2SO4 or a mixture thereof. 82. The method of embodiment 81, wherein the reagent is CO2. 83. The method of embodiment 81, wherein the reagent is H2SO4. 84. The method of any one of embodiments 64-83, wherein the electrolytic relithiation reaction is carried out 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 embodiments 64-83, wherein the electrolytic relithiation reaction is carried out by adjusting the cell current. 86. The method according to embodiment 85, wherein the electrolysis reaction in current-controlled mode can be carried out in direct current mode, pulse mode, whether in simple (unidirectional) mode or in reverse mode. 87. The method according to embodiment 85 or embodiment 86, wherein the electrolysis reaction in current-controlled mode can be carried out at a fixed frequency or at a variable frequency. 88. The method of any one of embodiments 47-63, wherein step a″) comprises (i) adding the partially or fully delithiated insertion material to a solution comprising a reducing agent and a relithiation salt in a solvent to allow relithiation of the partially or fully delithiated insertion material and production of a relithiated lithium insertion material. 89. The method of embodiment 88, further comprising: (ii) separating the relithiated lithium insertion material from the solution; and (iii) electrochemically treating the solution separated in step (ii) to regenerate the reducing agent. 90. The method of embodiment 88 or embodiment 89, wherein the relithiated salt is as described in any one of embodiments 70-74. 91. The method of any one of embodiments 88-90, wherein the reducing agent is the reducing member of a redox pair having a redox potential lower than the redox potential of the partially or fully delithiated intercalation material. 92. The method of embodiment 91, wherein the redox couple comprises an Fe(III) / Fe(II) complex. 93. 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)] + 93. The method of embodiment 92, wherein the hydroxybenzoate is hydroxybenzoate / [Fe(oxalate)]. 94. The method of any one of embodiments 88-93, wherein step (i) further comprises deoxygenating the solution. 95. The method of any one of embodiments 88-94, wherein step (i) and / or step (iii) is carried out in the absence of oxygen. 96. The method of any one of embodiments 88-95, further comprising adjusting the pH of the solution. 97. The method of any one of embodiments 88-96, wherein the solvent is an aqueous solvent. 98. The method of any one of embodiments 88-97, wherein step (iii) is carried out in an electrolytic cell by passing an electric current between at least one cathode and at least one anode. 99. The method of embodiment 98, wherein the electrolysis cell includes at least one ionic or nonionic separator installed between the anode and the cathode to protect the regenerated reducing agent. 100. The method of embodiment 98 or 99, wherein the electrolytic cell further comprises a system for maintaining a deoxygenated solution. 101. The method according to any one of embodiments 98-100, wherein step (iii) is carried out by adjusting the cell potential between the anode and the cathode or between the cathode and the reference electrode. 102. The method of any one of embodiments 98-100, wherein step (iii) is carried out by adjusting the cell current. 103. The method of embodiment 102, wherein the relithiation reaction in regulated current mode is carried out in direct current mode, pulse mode, whether in simple (unidirectional) mode or in reverse mode. 104. The method of embodiment 102 or embodiment 103, wherein the relithiation reaction in regulated current mode is carried out at a fixed frequency or at a variable frequency. 105. The method of any one of embodiments 47-104, further comprising washing and drying the current collector with lithium metal or its alloy or pre-lithiated electrode produced in step b). 106. The method of any one of embodiments 47-105, further comprising using the current collector with lithium metal or its alloy, 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 its alloy for pre-lithiating an electrode material, or as a source of lithium metal or its alloy for manufacturing an energy storage system. 107. The method of any one of embodiments 47-106, further comprising rolling the current collector with the lithium metal or its alloy to modify the morphology, density, or film thickness of the lithium metal or its alloy. 108. The method of any one of embodiments 47-107, further comprising treating the current collector with lithium metal or its alloy to have a 3D structure. 109. The method of any one of embodiments 47-108, further comprising treating the current collector with lithium metal or its alloy to improve its electrochemical performance in the battery. 110. The method of any one of embodiments 47-105, further comprising using a current collector with lithium metal or an alloy thereof as a lithium source to produce an organolithium compound. 111. The method of embodiment 110, wherein lithium metal or an alloy thereof is reacted with a reagent such as an alkyl halide to produce an organolithium compound. 112. The method of embodiment 111, further comprising transferring the current collector with lithium metal or its alloy produced in step b) to another reactor, preferably in a roll-to-roll mode, and reacting the lithium metal or its alloy with a reactant in the other reactor to produce an organolithium compound. 113. For prelithiating electrode materials, preferably for prelithiating anode materials, more preferably graphite, silicon, silicon oxide (SiO x 113. The method of any one of embodiments 47 to 112, wherein the electrode material is intended to be prelithiated, and the electrode material is used as a fabrication cathode. 114. The method of any one of embodiments 47 to 112, wherein the method is for producing lithium metal or an alloy thereof, preferably for producing lithium metal, preferably the lithium metal or an alloy thereof is produced by electrodeposition, and the current collector is used as a production cathode. 115. The method of embodiment 114, wherein the lithium metal or an 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 with lithium metal or an alloy thereof, produced by the method of any one of embodiments 47-115. 117. A lithium battery comprising a lithium electrode according to embodiment 116, preferably, the battery is a lithium-ion battery or an all-solid-state battery. In the accompanying drawings: [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 shows a schematic diagram of an embodiment of the method of the present invention using LiHCO as the relithiation salt. [Figure 2] FIG. 1 shows a schematic diagram of an embodiment of the method of the present invention using Li2SO4 as the relithiation salt. [Figure 3] 1 shows a double-sided manufacturing electrolysis cell with a multi-stage electrolysis structure. [Figure 4] Figure 1 shows the cell potential as a function of time (top black line) for galvanostatic electrodeposition of lithium metal as described in Example 4. The bottom grey line represents the applied current density. [Figure 5] Figure 1 shows the cell potential as a function of time (top black line) for galvanostatic electrodeposition of lithium metal in the button cell of Example 5. The bottom grey line represents the applied current density. [Figure 6] Chronocoulometry of the relithiation process of delithiated LiFePO4 (FP) on relithiated LiFePO4 (LFP), which is sometimes also called FePO4 or FP (even though it may contain residual lithium). [Figure 7] 1 shows a comparison of the X-ray diffraction spectra of a pristine LFP electrode, an FP electrode before relithiation, and an LFP electrode after relithiation. [Figure 8] A comparison of the cycling stability of cells with a commercially available lithium anode prepared by physical vapor deposition (PVD) (triangles) with that of (doubled) cells with an electrodeposited lithium (LiED) anode (from Example 4) (squares and diamonds) is shown. [Figure 9] The cell potential is shown as a function of time (top black line) for galvanostatic electrodeposition of lithium metal. The bottom grey line represents the applied current density. [Figure 10A] 1 shows the appearance of the electrodeposited lithium of Example 7 before calendering. [Figure 10B] 1 shows the appearance of the electrodeposited lithium of Example 7 after calendering. [Figure 11] 1 shows a scanning electron microscope (SEM) photograph of a cross section of the electrodeposited and calendered lithium of Example 7. The thickness of the thicker top layer, corresponding to the electrodeposited lithium, is 7.52 μm, while the thickness of the thinner bottom layer, corresponding to the copper foil, is 3.37 μm. [Figure 12] The cycling stability of the electrodeposited lithium of Example 7 is compared with that of a lithium foil prepared by PVD. [Figure 13] The cycling stability of lithium electrodeposited on various current collectors is compared. [Figure 14] Figure 8 shows the cell potential as a function of time (top black line) for the galvanostatic electrodeposition of lithium metal in Example 8.1. The bottom grey line represents the applied current density. [Figure 15] Figure 8 shows the cell potential as a function of time (top black line) for the galvanostatic electrodeposition of lithium metal in Example 8.2. The bottom grey line represents the applied current density. [Figure 16] Figure 8 shows the cell potential as a function of time (top black line) for the galvanostatic electrodeposition of lithium metal in Example 8.3. The bottom grey line represents the applied current density. [Figure 17] Figure 1 shows the cell potential as a function of time (top black line) for the galvanostatic electrodeposition of lithium metal in Example 9. The bottom grey line represents the applied current density. [Figure 18] 1 shows the appearance of the electrodeposited lithium of Example 9. [Figure 19] Figure 1 shows the cell potential as a function of time (top black line) for constant current relithiation of the LFP that was delithiated to form the LFP in Example 10. The bottom grey line represents the applied current density. [Figure 20] 1 shows the FTIR spectra of the delithiated (FP) and relithiated (LFP) electrodes of Example 10. [Figure 21]Figure 1 shows the cell potential as a function of electrodeposition time (LiED) for Example 10 (LiED of relithiated LFP, solid line) and Example 8.2 (LiED of pristine LFP, dotted line). [Figure 22] 1 shows the change in potential of the LTO working electrode during relithiation in Example 11. [Figure 23] 1 shows the anodic current linear sweep voltammetry curves of the relithiated LTO electrode of Example 11. [Figure 24] Compare the effects of various additives added to the electrolyte during lithium electrodeposition. [Figure 25] 1 shows a titration curve generated to determine the concentration of n-butyllithium in n-hexane (Example 13). [Figure 26] 1 shows galvanostatic prelithiation of a graphite anode using an LFP counter electrode as the lithium source. [Figure 27] Figure 1 shows the galvanostatic prelithiation of a SiOx anode using an LFP counter electrode as the lithium source. [Figure 28] The potential curves as a function of charge for the first formation cycle of a virgin graphite anode and a pre-lithiated anode are compared. [Figure 29] The potential curves as a function of charge for the first formation cycle of a virgin SiOx anode and a prelithiated anode are compared. DETAILED DESCRIPTION OF THE INVENTION

[0011] More particularly, the present invention relates to a relithiated lithium insertion material for producing lithium metal or an alloy thereof or for prelithiating an electrode material. In a related aspect, the present invention relates to the use of the relithiated lithium insertion material for producing lithium metal or an alloy thereof or for prelithiating an electrode material.

[0012] In certain embodiments of the present invention, the material / use is for producing lithium metal or alloys thereof. In certain embodiments, lithium metal is produced. In other embodiments, alloys are produced. In preferred embodiments, the lithium metal or alloys thereof is in the form of a film. Preferably, the lithium metal or alloys thereof are produced by electrodeposition.

[0013] In certain embodiments of the present invention, the material / use is for pre-lithiating an electrode material. The electrode material may be any electrode material that may experience active lithium loss during the first operating cycle of the battery. In certain embodiments, the electrode material may be graphite, silicon, silicon oxide (SiO x ), silicon-carbon composites, carbon nanotubes, or mixtures thereof.

[0014] Here, "lithium insertion material" refers to a material that contains lithium ions (Li + ) are materials used to reversibly contain lithium. Such materials are often used, for example, in the manufacture of cathodes for Li-ion batteries. + The insertion of ions is referred to herein as "lithiation" of the material. + The deintercalation of ions is referred to herein as "delithiation." Delithiation can be partial or complete. Complete delithiation refers to the removal of all Li ions that can be deintercalated under any particular set of conditions that may be applied. + Partial delithiation means that only a portion of these ions are deintercalated.

[0015] Here, "relithiated" refers to the lithiation of a lithium insertion material after partial or complete lithiation. Consequently, a "relithiated lithium insertion material" is a partially or fully delithiated lithium insertion material that has been relithiated.

[0016] Examples of partially or fully delithiated lithium insertion materials include lithium insertion materials deteriorated by lithium loss. Such materials are manufactured for the method of the present invention and can be re-lithiated and reused in the method of the present invention. Such delithiated lithium insertion materials can also be seen, for example, in used cathodes of used Li-ion batteries, leading to a decrease in capacity. When the partially or fully delithiated lithium insertion material is re-lithiated, at least some lithium ions are recovered, and as a result, some electrochemical properties are recovered. Preferably, the re-lithiated lithium insertion material has recovered at least 50%, preferably at least 75%, more preferably at least 85%, still more preferably at least 95%, and still more preferably at least 99% of the previously de-inserted lithium ions.

[0017] There is no particular limitation on the re-lithiated lithium insertion material.

[0018] In a preferred embodiment, the re-lithiated lithium insertion material is lithium phosphate or lithium oxide. In a preferred embodiment, the re-lithiated lithium insertion material is ·Li w FePO4 (where w ≤ 1.1, preferably w is 1), ·Li w Fe 1-x Mn x PO4 (where w ≤ 1.1, preferably w is 1, x is in the range of 0 < x ≤ 1, preferably in the range of 0.2 < x ≤ 0.4), ·Li w Mn2O4 (where w ≤ 1.1, preferably w is 1), ·Li w Mn 1.5 Ni 0.5 O4 (where w ≤ 1.1, preferably w is 1), ·Li 4+z Ti5O 12 (where z is in the range of 0 < z ≤ 3), or ·NMC (Li w Ni1-x-y Mn x Co y O2, wherein w≦1.3, preferably w is 1, x is in the range of 0≦x≦1, y is in the range of 0≦y≦1, z is in the range of 0≦z≦1, and M is aluminum, magnesium, titanium, niobium, zirconium, tungsten, molybdenum, yttrium, lanthanum, tantalum, or a mixture thereof. It should be noted that the lithium insertion material may contain excess lithium, meaning that its lithium content exceeds the stoichiometric ratio.

[0019] In a preferred embodiment, the relithiated lithium insertion material is Li w It is FePO4.

[0020] In a preferred embodiment, the relithiated lithium insertion material is made from a partially or fully delithiated lithium insertion material made by the method of the present invention. In another embodiment, the relithiated lithium insertion material is obtained from a spent electrode, for example, through battery recycling, and then relithiated.

[0021] Manufacturing Anodes The present invention also relates to a fabrication anode for producing lithium metal or its alloys or for prelithiating an electrode material, the anode comprising a relithiated lithium insertion material. This anode is referred to as a "fabrication anode" to distinguish it from another anode below (relithiated anode) used in an electrolytic relithiation reaction. In a related aspect, the present invention relates to the use of the relithiated lithium insertion material as an anode for producing lithium metal or its alloys or for prelithiating an electrode material.

[0022] In certain embodiments, the anode is intended to produce lithium metal or an alloy thereof. In certain embodiments, lithium metal is produced. In certain embodiments, lithium alloys are produced. Preferably, the lithium metal or an alloy thereof is in the form of a film. Preferably, the lithium metal or an alloy thereof is produced by electrodeposition.

[0023] In certain embodiments, the anode is intended for prelithiation of the electrode material, the electrode material being as defined above.

[0024] The relithiated lithium insertion material is as defined above.

[0025] In certain embodiments, the production anode is intended for an electrolytic reaction to produce lithium.

[0026] In certain embodiments, the fabricated anode further comprises a current collector, on which the relithiated lithium insertion material is deposited. The current collector may be made of any electronically conductive material, including any material used in battery current collectors. In certain embodiments, the current collector is a metal foil, preferably a foil made of copper, aluminum, stainless steel, titanium, or nickel, or made of a conductive carbon material, or is a polymer-based current collector. In the most preferred embodiment, the current collector is covered with a primer coat, such as a carbon-containing paint, to improve adhesion of the lithium insertion material. In a preferred embodiment, the current collector is a metal foil made of stainless steel or aluminum, preferably a carbon-coated aluminum foil.

[0027] In a preferred embodiment, the fabrication anode is in the form of a film.

[0028] Manufacturing Electrolysis Cell The present invention also relates to a manufacturing electrolytic cell for producing lithium metal or an alloy thereof or for prelithiating an electrode material, the manufacturing electrolytic cell comprising: a relithiated lithium insertion material used as a fabrication anode; a current collector used as a production cathode; A fabrication electrolyte is included between the fabrication cathode and the fabrication anode, the fabrication electrolyte including a fabrication lithium salt dissolved in a fabrication solvent.

[0029] Herein, these cells, cathodes, electrolytes, salts, and solvents are referred to as "production cells," "production cathodes," etc., respectively, to distinguish them from the cells, cathodes, electrolytes, salts, and solvents used in the electrolytic relithiation reaction, which are referred to as "relithiated cells," "relithiated cathodes," etc., respectively, and which are described below.

[0030] In a related aspect, the invention relates to the use of a production electrolytic cell to produce lithium metal or its alloys or to prelithiate electrode materials.

[0031] The relithiated lithium insertion material is as defined above.

[0032] The production anode is as defined above.

[0033] The manufacturing lithium salt can be any salt that is compatible with the lithium metal (or alloy) being manufactured. In certain embodiments, the manufacturing lithium salts include lithium (fluorosulfonyl)(trifluoromethanesulfonyl)imide, lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium difluorophosphate (LiDFP), lithium chloride (LiCl), lithium bromide (LiBr), lithium hexafluoroarsenate (LiAsF), lithium fluoroalkylphosphates [such as LiPF(CFCF)], lithium tetrakis(trifluoroacetoxy)borate (LiB(OCOCF)), lithium bis(1,2-benzenediolato(2-)-O,O′)borate LiB(CO), lithium difluoro(oxalato)borate (LiBF(CO)), ...tetrakis(trifluoroacetoxy)borate (LiB(OCOCF)), lithium bis(1,2-benzenediolato(2-)-O,O′)borate LiB(CO), lithium difluoro(oxalato)borate (LiBF(CO)), lithium tetrakis(trifluoroacetoxy)borate (LiB(CO)), lithium tetrakis(trifluoroacetoxy)borate (LiB(CO)), lithium tetrakis(trifluoroacetoxy)borate (LiB(CO)), lithium tetrakis(trifluoroacetoxy)borate (LiB(CO)), lithium tetrakis(trifluoroacetoxy)borate (LiB(CO)), lithium tetrakis(trifluoroacetoxy)borate (LiB(CO)), lithium tetrakis(trifluoroacetoxy x - (R x =C 2-4 The lithium salt may be a compound having a substituted or unsubstituted alkyl group, such as 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 manufacturing lithium salt is a combination of CF3SO3Li and LiFSi.

[0034] In certain embodiments, the manufacturing electrolyte further comprises one or more additives. Non-limiting examples of additives include additives that modify the morphology and / or properties of lithium metal or its alloys, additives that affect the phase nucleation energy, additives that affect the deposition potential of lithium metal or its alloys, and additives that affect the electrodeposition efficiency of lithium metal or its alloys. In certain embodiments, the additive(s) are: Cyclic unsaturated carbonates such as vinylene carbonate (VC), Halogenated cyclic carbonates such as fluoroethylene carbonate (FEC), ·nitrate, Lithium polymerization agents containing saturated or unsaturated hydrocarbon chains, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), lithium passivation compounds, and / or Alkaline salts of organic acids, such as lithium difluoro(oxalato)borate (LiDFOB) or lithium oxalate.

[0035] The manufacturing solvent may be any solvent commonly used in Li-ion batteries. In certain embodiments, the manufacturing solvent is an organic carbonate, an organic ester, an organic ether, an ionic liquid, or any combination thereof. In preferred embodiments, the manufacturing 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), a fluoroether, tetrafluoroethyl tetrafluoropropyl ether (TTE), tetraethylene glycol dimethyl ether (TEGDME), or any combination thereof.

[0036] In certain embodiments, the production electrolysis cell does not have a membrane separating the production anode from the production cathode.

[0037] In certain embodiments, the production electrolysis cell employs a roll-to-roll configuration. Indeed, membrane-less configurations of the cell can employ a multi-stage roll-to-roll configuration, such as that shown in Figure 3. In such embodiments, the cell may further comprise one or more calendering devices, such as, for example, a pair of spaced calender rolls, for densifying the electrodeposited lithium (or lithium alloy) film during its formation.

[0038] In certain embodiments, the production electrolytic cell is intended to prelithiate an electrode material, as defined above, for use as a production cathode. During use, the production electrolytic cell can introduce lithium into the electrode material.

[0039] In other embodiments, the production electrolytic cell is intended to produce lithium metal or an alloy thereof. The current collector is used as a production cathode. In certain embodiments, lithium metal is produced. In certain embodiments, lithium alloys are produced. Preferably, the lithium metal or an alloy thereof is in the form of a film. Preferably, the lithium metal or an alloy thereof is produced by electrodeposition. In use, the production electrolytic cell allows for the electrodeposition of a film of lithium metal or an alloy thereof onto the current collector used as the production cathode.

[0040] In a preferred embodiment, operating conditions such as stirring and / or temperature control are used to modify the morphology of the produced lithium metal / alloy.

[0041] In a preferred embodiment, the current collector used as a production cathode is in the form of a foil.

[0042] The current collector used as a production cathode can be made from any electronically conductive material, including any material used for current collectors in batteries. In certain embodiments, the current collector is made from one of copper, aluminum, protected aluminum, carbon, stainless steel, titanium, zinc, nickel, or alloys thereof, or is a metallized polymer-based current collector, or a combination thereof.

[0043] In a preferred embodiment, the current collector is made from passivated copper or aluminum.

[0044] The current collector used as a production cathode may or may not be protected by a protective layer. The surface of the current collector can be treated or modified to improve its lithophilicity. The surface of the current collector can 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 to increase the reaction rate when used, for example, in the production of organolithium compounds.

[0045] In certain embodiments, the manufacturing electrolyte further includes one or more alloying salts. An alloying salt is a salt of one or more metals capable of forming an alloy with lithium. When an alloying salt is used, a lithium alloy is produced at the cathode. In other embodiments, the manufacturing electrolyte does not include an alloying salt, and thus lithium metal, rather than a lithium alloy, is produced at the cathode.

[0046] In a preferred embodiment, the alloy comprises primarily lithium, hi a preferred embodiment, the alloy comprises at least about 80% w / w lithium, preferably at least about 85% w / w lithium, more preferably at least about 90% w / w lithium, and even more preferably at least about 95% w / w lithium, based on the total weight of the alloy.

[0047] In certain embodiments, the alloy salt is a salt of one or more of the elements sodium, potassium, magnesium, calcium, a transition metal, aluminum, gallium, or tin, preferably an aluminum or magnesium salt.

[0048] In certain embodiments, the alloy salt is a (fluorosulfonyl)(trifluoromethanesulfonyl)imide salt, a 2-trifluoromethyl-4,5-dicyanoimidazolate (TDI) salt, a 4,5-dicyano-1,2,3-triazolate (DCTA) salt, a bis(pentafluoroethylsulfonyl)imide salt (BETI), a difluorophosphate salt (DFP), a chloride salt, a bromide salt, a fluoride salt, a hexafluoroarsenate salt (AsF), a fluoroalkylphosphate salt, a tetrafluoroethylene ... trachys(trifluoroacetoxy)borate, bis(1,2-benzenediolato(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, triflate salt, or a salt of the formula BF2O4R x - (R x =C 2-4 It is a salt having an anion having alkyl.

[0049] Method for producing lithium metal / its alloys or for prelithiating electrode materials The present invention also relates to a method for producing lithium metal or an alloy thereof or for prelithiating an electrode material, the method comprising: a) providing a relithiated lithium insertion material; b) conducting an electrolytic reaction to produce lithium in a production electrolytic cell, the production electrolytic cell comprising: the relithiated lithium insertion material as a fabrication anode; a current collector or electrode material as a manufacturing cathode; a fabrication electrolyte between the fabrication cathode and the fabrication anode, the fabrication electrolyte including a fabrication lithium salt dissolved in a fabrication solvent; This allows for the electrodeposition of lithium metal or an alloy thereof onto a current collector to be used as a production cathode, or for lithium to be incorporated into an electrode material to be used as a production cathode, to produce a pre-lithiated electrode; thereby enabling the production of partially or fully delithiated lithium insertion materials.

[0050] In certain embodiments, the method is used to produce lithium metal or an alloy thereof. In certain embodiments, lithium metal is produced. In other embodiments, lithium alloys are produced. In all of these embodiments, the current collector is used as a production cathode. Preferably, the lithium metal or an alloy thereof is in the form of a film.

[0051] In another embodiment, the method is used to prelithiate an electrode material, the electrode material being as defined above, for use as a production cathode.

[0052] This method, and the materials, anodes, and cells (and applications) described in the previous sections, have several advantages. Avoiding the use of membranes in the production electrolysis cell, thereby reducing costs, avoiding contamination issues (especially water leaks) that can affect lithium purity, and avoiding downtime due to membrane maintenance. This allows for the use of multi-stage roll-to-roll constructions, potentially with calendering within the production electrolysis cell, resulting in a significant reduction in the space required for the process and an increase in production speed many times over. · It is possible to use spent cathode materials previously used in secondary batteries (to produce relithiated lithium insertion materials), allowing for the recycling of spent secondary batteries. The method may be a closed loop, thereby limiting environmental impact and ensuring safety. This method produces ultra-thin, homogeneous lithium metal electrodes of high purity at low cost without the need for additional purification steps. This method produces lithium film or foil without dissolving lithium. This method does not require high temperature electrolysis. The produced lithium can be used in the production of primary and secondary lithium-based batteries, as well as in the production of organolithium compounds and the prelithiation of electrode materials. For relithiation, the anodic reaction is the release of oxygen rather than chlorine (non-corrosive and easy to handle). The lithium salt used may be a cheap and easily purified lithium salt such as lithium carbonate, or it may be a lower purity lithium carbonate or other lithium salt.

[0053] In a preferred embodiment, the relithiated lithium insertion material of the present method is as defined in the previous section.

[0054] In a preferred embodiment, the fabrication anode of the present method is as defined in the previous section.

[0055] In a preferred embodiment, the manufacturing electrolytic cell of the present method is as defined in the previous section.

[0056] Preferably, the current collector with lithium metal or its alloy, or the pre-lithiated electrode, is washed, for example with an organic solvent, and dried prior to use. Thus, in one embodiment, the method further comprises washing and drying the current collector with lithium metal or its alloy, or the pre-lithiated electrode produced in step b).

[0057] Step b) In step b), the relithiated lithium insertion material serves as an anode to provide lithium ions for the electrodeposition of lithium metal or its alloys or for the prelithiation of a cathode material. + to provide.

[0058] Lithium metal or its alloys are deposited on a current collector that serves as the cathode. Lithium metal or its alloys are typically electrodeposited onto the current collector in the form of a thin, generally pure, film. Alternatively, lithium is incorporated into the electrode material that serves as the cathode.

[0059] The electrochemical reactions on the cathode and anode in an electrolytic production cell are as follows: Cathodic reaction: [C1] Li + +e - →Li Anode reaction (when LiFePO4 is used as a relithiated lithium insertion material): [Case 2] LiFePO4 → FePO4+e - +Li +

[0060] A partially or fully delithiated lithium insertion material is produced in the anode (FePO4 in the above example) and is used as a starting material in step a) to provide a relithiated lithium insertion material, which can then be reused in step b).

[0061] In certain embodiments, the electrolytic reaction to produce lithium is carried out by adjusting the cell potential between the production anode and the production cathode or between the production cathode and a reference electrode.

[0062] In certain embodiments, the electrolysis reaction for producing lithium is conducted by modulating the cell current. In certain embodiments, the electrolysis reaction for producing lithium in modulated current mode can be conducted in direct current mode, pulsed mode, whether in simple (unidirectional) mode or reverse mode. Similarly, the electrolysis reaction for producing lithium in modulated current mode can be conducted at a fixed frequency or a variable frequency.

[0063] In certain embodiments, step b) is performed in a roll-to-roll configuration. Indeed, the membrane-free configuration of the electrochemical manufacturing cell in step b) allows for the use of a multi-stage roll-to-roll configuration, such as that shown in Figure 3. In such embodiments, the cell may further comprise one or more calendering devices, such as, for example, spaced calender rolls, to densify the electrodeposited lithium film during its formation.

[0064] Step a) As previously mentioned, a relithiated lithium insertion material is a partially or fully delithiated lithium insertion material that has been relithiated.

[0065] The partially or fully delithiated lithium insertion material is not particularly limited. It must be selected so as to be stable under the conditions (such as the electrolyte) used for relithiation. In a preferred embodiment, the partially or fully delithiated lithium insertion material is lithium phosphate or partially or fully 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 fully delithiated lithium insertion material is a partially or fully delithiated Li w FePO4 (preferably w is 1).

[0066] In a particular embodiment, step a) is performed in a roll-to-roll configuration.

[0067] In certain embodiments, step a) comprises: a') providing a partially or fully delithiated lithium insertion material; a'') relithiating the partially or fully delithiated lithium insertion material to produce a relithiated lithium insertion material.

[0068] The relithiated lithium insertion material is then used in step b).

[0069] In a preferred embodiment, the relithiated lithium insertion material is washed, preferably washed and dried, before being used in step b).

[0070] In certain embodiments, the partially or fully delithiated lithium insertion material is obtained from recycled spent batteries.

[0071] As noted above, in certain embodiments (preferably when the method of the present invention is iterative or continuous), the partially or fully delithiated lithium insertion material of step a') can be that produced in step b). As a result, in certain embodiments, the method further comprises step c) of repeating steps a) and b) one or more times and using the partially or fully delithiated lithium insertion material produced in step b) in steps a') and a'').

[0072] The partially or fully delithiated lithium insertion material can be relithiated in step a'') by any method known in the art.

[0073] Relithiation by electrolysis using lithium salt electrolytes In a preferred embodiment, step a″) comprises carrying out the electrolytic relithiation reaction in an electrolytic relithiation cell, the electrolytic relithiation cell comprising: a partially or fully delithiated intercalation material as a relithiated cathode; a relithiated anode; and a relithiated electrolyte between the relithiated cathode and the relithiated anode; the relithiated electrolyte comprises a relithiated lithium salt dissolved in a relithiated solvent; This allows for the relithiation of partially or fully delithiated insertion materials and the production of relithiated lithium insertion materials.

[0074] In this electrolysis reaction, the relithiated lithium salt is converted into lithium ions. + The lithium intercalation material is used as a source of lithium, and the partially or fully delithiated intercalation material is used as the cathode. The general reaction is: Anode reaction (when FePO4 is used as a delithiated lithium insertion material): [C3] 2Li + +2e - +2FePO4 → 2LiFePO4 Anode reaction (when LiHCO3 is used as the relithiated lithium salt): [C4] 2HCO3 - -2e - →1 / 2O2+H2O+2CO2

[0075] The relithiation solvent can be any solvent, or mixture thereof, capable of dissolving the lithium salt and supporting a compatible anodic reaction, hi a preferred embodiment, the relithiation solvent is water, which is an advantage of the present invention.

[0076] The anode material is not particularly limited. In certain embodiments, the relithiated anode is made of a material that is compatible with the anode reaction, preferably a material that is compatible with the oxygen-releasing reaction. In preferred embodiments, the relithiated anode is made of lead, platinum, titanium, another inert metal, or one of their alloys, or graphite. In preferred embodiments, the relithiated anode is a dimensionally stable anode.

[0077] In certain embodiments, the relithiation electrolyte further comprises one or more additives. Such additives typically do not participate in the electrolytic relithiation reaction. Non-limiting examples of additives include additives that improve the conductivity of the relithiation electrolyte. In certain embodiments, the additive(s) 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).

[0078] The relithiation salt can be any lithium salt that can be dissolved in a relithiation electrolyte, for example, LiFSI or LiTFSI.

[0079] In the most preferred embodiment, the relithiated salt is a low cost lithium salt. Examples of low cost lithium salts include: Lithium salts extracted from mines, e.g. Li2CO3, Economically prepared lithium salts from mined salts, e.g. LiHCO3, which can be prepared from Li2CO3 as shown in Example 1, Li2SO4, which can be prepared from Li2CO3 as shown in Example 2, LiOH, which can be prepared by electrolysis of LiCl, Li2SO4 or LiHCO3, or from Li2CO3 by metathesis with calcium hydroxide, LiNO3, which can be prepared by treating Li2CO3 or LiOH with nitric acid, LiCH3COO, which can be prepared by treating Li2CO3 with acetic acid, and Li2C2O4, which can be prepared by treating Li2CO3 with oxalic acid, Lithium salts produced during the hydrometallurgical recycling of used lithium batteries, including, for example, many of the salts already mentioned above, as well as Lithium salts recovered from lithium-containing solutions, such as geothermal brines, salt lake brines, and solutions from lithium ore processing and lithium battery recycling processes, including, for example, many of the salts already listed above.

[0080] In preferred embodiments, the relithiated salts are easy to purify. As an example, Li2CO3 is easy to purify due to its low solubility (impurities precipitate from solution while remaining dissolved) and easy to dry due to its low hygroscopicity (unlike LiCl, which is very difficult to purify due to its high solubility in water and very difficult to dry due to its high hygroscopicity).

[0081] In a preferred embodiment, the relithiated salt is LiCO, LiHCO, LiOH, LiNO, LiOH, LiSO, LiCHCOO, LiFSI, LiTFSI or LiCO, or a mixture thereof; preferably, the relithiated salt is LiHCO, LiSO, or a mixture thereof; more preferably, the relithiated salt is LiSO.

[0082] In certain embodiments in which the relithiation solvent is water, it may be advantageous for the relithiation salt to be a water-soluble relithiation salt. In the most preferred embodiment, the relithiation salt is a water-soluble relithiation salt having a water solubility greater than that of LiHCO. Non-limiting examples of such salts include LiNO, LiSO, and LiCHCOO. Converting LiCO to these salts may offer certain advantages over using LiCO as LiHCO. For example, electrolytic relithiation cells can be operated at higher temperatures (because, unlike LiHCO, the solubility of these salts increases with temperature), which, combined with their higher solubility, can help operate the electrolytic cell at higher current densities (improving cell productivity and lowering investment costs).

[0083] In certain embodiments, the relithiation salt is produced in situ, i.e., within the electrolytic relithiation cell. In such embodiments, the method comprises adding a lithium precursor and a reagent to the electrolytic relithiation cell and reacting them to form the relithiation salt. In a preferred embodiment, the lithium precursor and reagent can be added to a salt-forming compartment of the electrolytic relithiation cell that is in fluid communication with the main compartment of the electrolytic relithiation cell, the main compartment containing the relithiated cathode and the relithiated anode.

[0084] In certain embodiment variations, the relithiation salt is simply added to the electrolytic relithiation cell. This means that the relithiation salt is prepared before being added to the electrolytic relithiation cell. In such embodiments, the method may include 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.

[0085] In either case, the choice of lithium precursor and reagent will, of course, depend on the desired relithiation salt. For example, LiHCO3, Li2SO4, LiNO3, and LiCH3COO may be prepared by reacting Li2CO3 with CO2, H2SO4, nitric acid, or acetic acid, respectively. Thus, in such embodiments, the lithium precursor is Li2CO3, LiOH, or a mixture thereof, as appropriate. Similarly, in such embodiments, the reagent is CO2, H2SO4, nitric acid, acetic acid, oxalic acid, or the acid form of a sulfonylimide salt, as appropriate, or a mixture thereof. 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 another preferred embodiment, the reagent is H2SO4.

[0086] Interestingly, when LiHCO3 is used as the relithiation salt, the anode reaction in the relithiation cell produces CO2, which can be recycled to produce more LiHCO3 from Li2CO3.

[0087] It is also interesting to note that when Li2CO3 is used as the lithium precursor in lithium electrolytes containing salts such as LiNO3, Li2SO4, or LiCH3COO as relithiation salts, there is no need to add acid to replace the H+ ions consumed during the conversion of the carbonate salt, as the H+ ions are regenerated at the anode.

[0088] In certain embodiments, the electrolytic relithiation reaction is carried out by adjusting the cell potential between the relithiated anode and the relithiated cathode, or between the relithiated cathode and a reference electrode.

[0089] In certain embodiments, the electrolytic relithiation reaction is carried out by modulating the cell current. In certain embodiments, the electrolytic reaction in modulated current mode can be carried out in direct current mode, pulsed mode, whether in simple (unidirectional) mode or reverse mode. Similarly, the electrolytic reaction in modulated current mode can be carried out at a fixed frequency or a variable frequency.

[0090] Relithiation with reducing agents In certain embodiment variations, step a″) comprises carrying out a relithiation reaction as described in WO2021 / 092692, which is incorporated herein by reference.

[0091] In a preferred embodiment, the method comprises (i) adding a partially or fully delithiated insertion material to a solution containing a reducing agent and a relithiation salt in a solvent, thereby allowing for the relithiation of the partially or fully delithiated insertion material and producing a relithiated lithium insertion material. The reaction is as follows: [5] 2Li ++2R-Fe 2+ +2FePO4 → 2LiFePO4 + 2R'-Fe 3+ where R and R' are anionic molecules or complexing agents.

[0092] In certain embodiments, the method further comprises (ii) separating the relithiated lithium insertion material from the solution, and preferably (iii) electrochemically treating the solution separated in step (ii) to regenerate the reducing agent.

[0093] The relithiated salt is as described in the previous section.

[0094] In certain embodiments, the reducing agent is the reducing element of a redox pair that has a lower redox potential than the partially or fully delithiated intercalation material.

[0095] According to one embodiment, the redox couple is, for example, an Fe(III) / Fe(II) complex, such as [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)].

[0096] According to one embodiment, step (i) further comprises deoxygenating the solution.

[0097] In one embodiment, steps (i) and / or (iii) are carried out in the absence of oxygen.

[0098] In one embodiment, the method further comprises adjusting the pH of the solution to a pH suitable for the electrochemically active material of step (i) (e.g., for FePO4, the pH is adjusted to 5-9, preferably 6-7.5).

[0099] In another embodiment, the solvent is an aqueous solvent.

[0100] According to one embodiment, the electrochemical treatment step (iii) is carried out in an electrolysis cell by passing an electric current between at least one cathode and at least one anode. The reaction occurring in step (iii) is as follows: Cathodic reaction: [6] 2R-Fe 3+ +2e - →2R'-Fe 2+ Anode reaction: [7] 2OH - -2e - →1 / 2O2+H2O

[0101] In one embodiment, the electrolytic cell comprises at least one ionic or non-ionic separator installed between the anode and cathode to protect the regenerated reducing agent. In another embodiment, the electrolytic cell further comprises a system that allows the solution to be maintained in a deoxygenated state, for example, a system that maintains gases such as carbon dioxide, nitrogen, argon, etc., in the absence of oxygen within the electrolytic cell.

[0102] In certain embodiments, step (iii) is carried out by adjusting the cell potential between the anode and the cathode or between the cathode and a reference electrode.

[0103] In certain embodiments, step (iii) is performed by modulating the cell current. In certain embodiments, the relithiation reaction in modulated current mode can be performed in direct current mode, pulsed mode, whether in simple (unidirectional) mode or reverse mode. Similarly, the relithiation reaction in modulated current mode can be performed at a fixed frequency or a variable frequency.

[0104] Use of the current collector and / or prelithiated electrode with lithium metal or its alloy produced in step b) The current collector and prelithiated electrode with lithium metal or its alloy produced in step b) can be used for many purposes.

[0105] In certain embodiments, the current collector with lithium metal or its alloy and / or the pre-lithiated electrode comprises: as a negative electrode in primary or secondary lithium batteries, preferably lithium-ion batteries or all-solid-state batteries, As a source of lithium metal or its alloys for prelithiation of electrode materials; and Used as a source of lithium metal or its alloys for manufacturing energy storage systems.

[0106] In certain embodiments, the current collector with lithium metal or its alloy is used as a source of lithium metal or its alloy for the preparation of organolithium compounds.

[0107] In certain embodiments, the current collector with 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. When the rolling temperature exceeds the melting point of lithium, a substrate with high lithophilicity can be used. Non-limiting examples of such substrates include silicon, tin, zinc, aluminum, ZnO, CuO, CuO, and CrO.

[0108] In certain embodiments, current collectors with lithium metal or its alloys are engineered to have 3D structures that can be used to improve the electrochemical performance of the lithium layer in a battery or to enhance reaction rates when used in the preparation of organolithium compounds.

[0109] In certain embodiments, the current collector with lithium metal or its alloy is surface treated to improve its electrochemical performance in the battery. For example, a thin layer of an element such as zinc or aluminum or one of their alloys can be deposited on the lithium layer. Different deposition methods can be used, such as physical vapor deposition (PVD) or spray coating.

[0110] In other embodiments, the current collector with lithium metal or its alloy is used to produce an organolithium compound. In such a preferred embodiment, the organolithium compound is produced by reacting with a reagent such as an alkyl halide. Such compounds are important reagents used as polymerization initiators in the production of elastomers or as strong base reagents in the synthesis of organic and pharmaceutical molecules. For example, 1-chlorobutane dissolved in an organic solvent (e.g., cyclohexane) can be reacted with the electrodeposited lithium metal or its alloy to produce n-butyllithium. In a more specific embodiment, the method further comprises transferring the current collector with lithium metal or its alloy produced in step b) to another reactor, preferably in a roll-to-roll mode, and reacting the electrodeposited lithium metal or its alloy with reactants in the other reactor to produce the organolithium compound.

[0111] The lithium electrode produced by the above method The present invention also relates to a lithium electrode comprising a current collector bearing lithium metal or an alloy thereof as described above (i.e., produced by the above method).

[0112] The present invention also relates to a lithium battery comprising this lithium electrode. In a preferred embodiment, the lithium battery is a lithium-ion battery or an all-solid-state battery.

[0113] definition In the context of describing the present invention (particularly in the context of the claims which follow), use of the terms "a," "one," "a kind," and "said" and similar referents are to be construed as encompassing both the singular and the plural, unless otherwise stated herein or clearly contradicted by context.

[0114] The terms "comprise," "have," "comprise," and "include" are to be construed as open terms (i.e., meaning "including, but not limited to") unless otherwise specified. In contrast, the phrase "consisting of" excludes unspecified elements, steps, ingredients, etc. The phrase "consisting essentially of" limits the scope of the invention to specified materials or steps and those that do not materially affect the basic novel feature(s) of the invention.

[0115] The recitation of ranges of values ​​herein is intended to serve as a shorthand method of referring individually to each individual value falling within the range, unless otherwise stated, and each individual value is incorporated herein as if it were individually set forth herein. Any subset of values ​​within a range is also incorporated herein as if it were individually set forth herein.

[0116] All methods described herein can be performed in any suitable order unless otherwise indicated or clearly contradicted by context.

[0117] The use of any or all of the examples or exemplary language (e.g., "etc.") set forth herein is intended only to more clearly describe the invention and does not limit the scope of the invention unless specifically stated.

[0118] No language in the specification should be construed as indicating any non-claimed element as essential to the actual practice of the invention.

[0119] Here, the term "about" has its ordinary meaning, which in certain embodiments may mean plus or minus 10% or plus or minus 5% of the qualified numerical value.

[0120] Unless otherwise defined, 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.

[0121] Further objects, advantages and features of the present invention will become more apparent from the following non-restrictive description of specific embodiments thereof, given by way of example only with reference to the accompanying drawings.

[0122] Description of exemplary embodiments The present invention is further illustrated by the following non-limiting examples.

[0123] Example 1 - Apparatus for carrying out the process of the present invention using LiHCO3 produced in situ as the relithiated salt. A schematic diagram of one embodiment of the method of the present invention is shown in FIG.

[0124] The electrolytic relithiation reaction is carried out in an electrolytic relithiation cell (10) containing a relithiation electrolyte and equipped with an agitator (12). In Figure 1, the relithiation electrolyte contains LiHCO as the relithiation salt.

[0125] The relithiation salt, LiHCO, is produced in the electrolytic relithiation cell (10) by reacting a lithium precursor, i.e., LiCO powder (14), with a reagent, in this case CO, which is added to the electrolyte using a bubbler (16). A wall (18) separates the electrolytic relithiation cell (10) into a salt-forming compartment (20) and a main compartment (22), each fluidly connected to the other.

[0126] The main compartment (22) of the electrolytic relithiation cell (10) contains a relithiated anode (24) and a partially or fully delithiated insertion material (26) that functions as the relithiated cathode. After the electrolytic relithiation reaction, the partially or fully delithiated insertion material (26) is relithiated to form a relithiated lithium insertion material (28). In this example, LiFePO4 on a metal foil (LFP) is used as the insertion material that is partially or fully delithiated and relithiated.

[0127] This step is performed in a roll-to-roll configuration: partially or fully delithiated intercalation material (26) provided by roll (30) is introduced into electrolytic relithiation cell (10), and relithiated lithium intercalation material (28) is extracted from electrolytic relithiation cell (10) and collected on roll (32) with the aid of intermediate rolls (34, 36, 38, and 40). A series of washing, rinsing, dehydration, and drying steps can be included in the roll-to-roll unit.

[0128] The roll (32) of relithiated lithium insertion material (28) is transferred to a production electrolytic cell (42), as shown by arrow B. The production electrolytic cell (42) uses the relithiated insertion material (28) as the production anode, a current collector (44) as the production cathode, and a production electrolyte. In this example, the current collector (44) is treated or untreated copper foil.

[0129] In the production electrolysis cell (42), lithium is electrodeposited onto a current collector (44) to produce a lithium-coated current collector (46), and the relithiated lithium insertion material (28) is delithiated (partially or completely) to regenerate the lithium insertion material (28), which can then be returned to the electrolytic relithiation cell (10) for relithiation, as indicated by arrow A.

[0130] This step is similarly performed in a roll-to-roll configuration. Relithiated lithium intercalation material (28) is supplied by roll (32), and partially or fully delithiated intercalation material (26) is collected on roll (30) with the aid of intermediate rolls (48, 50, 52, and 54). Similarly, current collector (44) is supplied by roll (56), and lithium-coated current collector (46) is collected on roll (58) by intermediate rolls (60, 62, and 64). A series of washing, rinsing, dewatering, and drying steps can be included in the roll-to-roll unit.

[0131] The lithium coated current collector (46) can be used or processed in a variety of ways. Arrow C indicates that a roll (58) of lithium coated current collector (46) can be cold rolled using cold rolls (60) to form a cold rolled lithium coated current collector (62) that is collected on roll (64) with the aid of intermediate rolls (66, 68). Arrow D indicates that a roll (58) of lithium coated current collector (46) can be hot rolled with the aid of hot rolls (70) to form a hot rolled lithium coated current collector (72) that is collected on roll (74) with the aid of intermediate rolls (76, 78).

[0132] In Figure 1, the intercalation material used in the lithium production step is LiFePO4 (LFP) on an aluminum substrate. The produced delithiated intercalation material (FP in this figure) is returned to the relithiation step and relithiated in the cathodic reaction in an aqueous medium, while oxygen release is the anodic reaction, as follows: Reaction 1 (cathodic reaction): [8] 2Li + +2e - +2FePO4 → 2LiFePO4 Reaction 2 (anodic reaction): [9] 2HCO3 - →1 / 2O2+H2O+2CO2+2e -

[0133] The source of lithium ions in this case is Li2CO3, which is dissolved in water in the form of LiHCO3 by bubbling CO2 into a suspension of Li2CO3 in water according to the following reaction: Reaction 3: [C10] Li2CO3+CO2+H2O→2LiHCO3

[0134] The advantage of dissolving Li2CO3 in the form of LiHCO3 is the higher solubility of LiHCO3 compared to Li2CO3.

[0135] Example 2 - Apparatus for carrying out the process of the present invention using in situ produced Li2SO4 as the relithiated salt Figure 2 shows a further embodiment of the method of the present invention based on the conversion of Li2CO3 to Li2SO4. Figure 2 is therefore similar to Figure 1, except that there is no bubbler and the relithiation electrolyte in the electrolytic relithiation cell (10) is different. The source of lithium ions in this case is Li2CO3, which is dissolved in water as Li2SO4 by reacting with H2SO4 according to the following reaction: Reaction 6: [C11] Li2CO3+H2SO4→Li2SO4+CO2+H2O

[0136] The cathodic reaction is the same as in the LiHCO3-based electrolyte (Example 1). However, in the anodic reaction, in addition to the evolution of oxygen, H + Ions are produced, thereby contributing to the regeneration of H2SO4 required for the conversion of Li2CO3 to Li2SO4. Reaction 7 (Cathode Reaction): [C12] 2Li + +2e - +2FePO4 → 2LiFePO4 Reaction 8 (anodic reaction): [C13] H2O-2e - →1 / 2O2+2H +

[0137] As a result, when Li2CO3 is added to the dedicated compartment of an electrolytic relithiation cell, H + Because ions are continuously produced at the anode, there is no need to add acid to the solution while Li2CO3 powder is continuously added to the cell.

[0138] Example 3: Electrodeposition cell with roll-to-roll structure 3 shows a further embodiment of an apparatus for carrying out the method of the present invention. In this case, the electrodeposition of lithium (step b) is carried out in a roll-to-roll configuration. One advantage of the present invention is that the absence of a membrane in the production electrolysis cell (42) allows the use of a multi-stage electrolysis configuration, which is very difficult to achieve if the lithium electrolysis cell must have separate anolyte and catholyte compartments, as described in US Patent 2021 / 0381115 A1 and US Patent 2022 / 0367874 A1.

[0139] In Figure 3, two rolls (32) supply the relithiated lithium intercalation material (28) to the production electrolysis cell (42). Similarly, two rolls (30) collect the partially or fully delithiated intercalation material (26). This is accomplished by several intermediate rolls (76). Additionally, current collector (44) is supplied by roll (56), and lithium-coated current collector (46) is collected on roll (58) by intermediate roll (78) and a pair of calendar rolls (80).

[0140] In fact, the cell also includes several pairs of calender rolls that allow the lithium metal layer to be densified during electrodeposition while still immersed in the electrolyte, which also allows the lithium film to have a high purity with a minimum of inclusions.

[0141] Example 4: Thin film electrodeposition of lithium in pocket cells Using LFP as a lithium ion source in a pocket cell assembly, a thin film of lithium was electrodeposited onto an ultra-thin current collector, and a lithium layer approximately 11.5 μm thick was confirmed.

[0142] Thin films of lithium metal were obtained by electrodeposition in a lithium double salt electrolyte dissolved in a solvent containing a carbonate base. The electrolyte was prepared by mixing ethylene carbonate (EC) with diethylene carbonate (DEC) in a 50 / 50 volume ratio in an argon-filled glove box. Lithium triflate (LiCF3COO) and lithium bis(fluorosulfonyl)imide (LiFSI) were then added to the solvent mixture at concentrations of 0.9 M and 0.1 M, respectively. The suspension was vigorously stirred until the salts were completely dissolved. To ensure the stability of the lithium-containing electrolyte and remove all traces of water, small strips of bare lithium metal were immersed in the electrolyte for at least 24 hours before use.

[0143] The LiFePO4 anode (LFP) was prepared by mixing the initial carbon-coated LFP, conductive carbon materials (carbon fiber (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) using a planetary centrifugal mixer until a completely uniform suspension was obtained. The suspension was applied to 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 roll calendering. The total specific charge of the electrode was 10 mg / cm. 2 is.

[0144] The electrodeposition of lithium was carried out in a pocket cell under galvanostatic conditions. The cell was assembled with a 4.5 μm thick dry copper foil as the cathode, the aforementioned LFP coated on aluminum foil as the anode, and a polypropylene (PP) film (Celgard 3501) as the separator. The two electrodes were 25.5 cm 2The pocket cell was filled with the pre-prepared electrolyte, sealed under vacuum, and placed between press plates, which compressed the pocket cell to approximately 75 psi. Galvanostatic electrolysis was performed at 0.5 mA / cm at 25°C. 2 The plating sequence was performed at a constant current of 0.05 V, and the total charge passed was approximately 129 C. The applied current and response potential for this plating sequence are shown in Figure 4.

[0145] After electrodeposition was complete, the lithium cathode was recovered by opening the pocket cell in the drying room hood. The copper / lithium electrode was washed three times with tetrahydrofuran (THF) and once with dimethoxyethane (DME). All solvents used were anhydrous. The lithium was then calendered between two stainless steel rolls at a speed of 10 mm / s at room temperature, while the electrode was placed between an 11 μm copper foil and a 20 μm polypropylene (PP) foil, with another 11 μm copper foil on top to protect the integrity of the lithium. The calendered lithium was then placed under vacuum for 12 hours to ensure evaporation of all DME. The resulting thin electrode foil consisted of an approximately 11.5 μm thick lithium layer on a 4.5 μm copper foil.

[0146] Example 5: Relithiation of LFP anodes In this example, a delithiated LFP (FP) electrode was obtained from a button cell, lithium was deposited under conditions similar to those in Example 4, and then relithiated in aqueous LiSO electrolyte, thereby confirming complete relithiation of the electrode in aqueous media.

[0147] The initial LFP electrode used during lithium plating consisted of a 16 mm diameter disk made of a mixture of LFP, conductive carbon, and PVDF coated on 15 μm aluminum foil, as described in Example 4, with a net charge of 9.1 mg / cm. 2Considering the theoretical capacity of 170 mAH / g LFP, the LFP anode has a charge capacity of 3.02 mAh. Lithium was then transferred from the LFP anode to a 4.5 μm copper foil cathode in a double salt electrolyte at 1 mA / cm as described in Example 4. 2 The LFP electrodeposited into a CR2032 button cell by discharging at a constant current of 0.05V for 1.29 hours. Figure 5 shows the change in potential recorded during this electrolysis versus time. The total charge passed through the cell was 2.6 mAh. At this point, based on coulomb calculations, the LFP electrode was 86% discharged.

[0148] In the second step, the delithiated LFP electrodes (called FP electrodes) were retrieved from the button cells, rinsed three times with THF and once with hexane, dried, and then relithiated. FP electrodes had an active surface of 1 cm. 2 The electrode was assembled in a holder. A 0.25 M Li2SO4 solution was prepared from ACS-grade lithium sulfate and demineralized water and adjusted to pH 6 with dilute H2SO4. Relithiation of the FP electrode was achieved by placing the FP cathode and a dimensionally stable anode (DSA) in lithium sulfate electrolyte. A constant potential of -0.05 V relative to the NHE was applied between the cathode and an Ag / AgCl reference electrode (3.5 M KCl). After 1 h, a total charge of 1.77 mAh had passed through the FP electrode. Figure 6 shows the accumulated charge as a function of time. The degree of conversion (from FP to LFP) of the electrode before and after relithiation was confirmed by X-ray diffraction (XRD) analysis, as shown in Figure 7. The spectrum of the electrode before relithiation indicates a 12.5% ​​partially delithiated electrode, which is consistent with the Coulombic electrodeposition data for lithium. The spectrum of the electrode after relithiation is similar to that of the initial LFP, thereby confirming complete relithiation of the electrode.

[0149] Example 6: Electrochemical properties of electrodeposited lithium The lithium-coated copper foil electrode prepared in Example 4 was used as the negative electrode in a rechargeable lithium battery. It was confirmed that the button cell prepared with electrodeposited lithium had significantly higher charge-discharge stability than the cell prepared with commercially available ultra-thin lithium foil prepared by PVD.

[0150] First, a lithium anode disk with a diameter of 14 mm was punched from the calendered lithium obtained in Example 4 between two sheets of PP foil.

[0151] The cathode was prepared by mixing Li(Ni) using a Thinky™ centrifugal mixer. 0.8 ,Mn 0.1 ,Co 0.1 A suspension was prepared by mixing 94% w / w, 3% w / w, 2% w / w, and 1% w / w of PVDF, Denka Black, and graphite in NMP. The resulting suspension was applied to carbon-coated aluminum. The coating was dried at 130°C and had a coating density of 3.3 g / cm. 3 The resulting cathode foil was dried again under vacuum at 120° C. for 12 hours.

[0152] A 14 mm diameter disk was punched from the cathode foil and attached to a stainless steel CR2032 button cell. The above-mentioned calendered 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 fabricated in this way.

[0153] The cells were cycled for three cycles at a charge / discharge rate of C / 10 at a temperature of 25°C for formation, and then cycled at a rate of C / 3 for stability testing. + / Li 0 The voltages were set to 2.7V and 4.2V.

[0154] To compare the performance of electrodeposited lithium with that of commercially available ultrathin lithium foils, reference cells were fabricated using commercially available 5 μm-thin lithium foils deposited directly on copper foils by PVD as the anode. These cells were tested against the same NMC under the same conditions. The specific capacity as a function of charge / discharge cycles is shown in Figure 8.

[0155] From Figure 8, it can be seen that the two button batteries prepared with electrodeposited lithium exhibited much higher charge-discharge stability than the two batteries prepared with the commercial ultrathin lithium foil prepared by PVD mentioned above.

[0156] Example 7: Electrodeposition of thin lithium on copper foil in a membrane-free electrochemical cell An undivided beaker-type electrochemical cell (without a membrane separating the cathode and anode compartments) (Tait cell from Ametek® SI) was used to electrodeposit a thin film of lithium onto a copper foil (cathode). The resulting lithium was then used as the negative electrode in a rechargeable lithium battery. It was confirmed that the method of the present invention can be carried out under the following conditions: 1) in a membrane-free electrochemical cell, and 2) at high current densities (4 mA / cm). 2 )in the case of.

[0157] 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 (6.5 cm internal diameter) placed on the copper foil, and a top plate that secures the assembly with a long screw with a nut. A gasket ensures a tight seal between the copper foil and the glass body.

[0158] Electrodeposition was carried out in an argon-filled glove box (HO<0.1 ppm, O<0.1 ppm) using an electrolyte consisting of ethylene carbonate (EC) and diethylene carbonate (DEC) in a 50 / 50 volume ratio, with electrolyte salts of 0.6 M lithium triflate (LiCFCOO) and 0.4 M lithium bis(fluorosulfonyl)imide (LiFSI). The anode was a 25 cm2 electrode coated with an LFP-based slurry with the same formulation as described in Example 4. 2 The active material charge is 23 mg / cm. 2 The anode was attached to a stirring shaft and placed at a distance of 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 galvanostatic electrolysis was carried out at room temperature with an anode rotation speed of 50 rpm and a current of 4 mA / cm 2 The current was applied for 22 minutes at a constant current density of 0.05V. Figure 9 shows the change in cell potential as a function of time.

[0159] The resulting electrodeposited lithium was washed and calendered using the same steps as in Example 4, before thickness measurements, which showed a lithium thickness of about 9 μm. The appearance of the deposit before and after calendering is shown in Figures 10a and 10b, and Figure 11 shows a cross section of the calendered lithium under a scanning electron microscope.

[0160] The resulting lithium was then used as the negative electrode in a rechargeable lithium battery. First, a lithium anode disk with a diameter of 14 mm was cut from the calendered lithium between two pieces of PP foil.

[0161] The cathode was prepared by mixing LFP, PVDF, Denka black, and graphite in NMP in proportions of 89% w / w, 5% w / w, 3% w / w, and 3% w / w, respectively, using a Thinky™ 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.

[0162] A 14 mm diameter disk was cut from the cathode foil and attached to a stainless steel CR2032 button cell. The calendered 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 (1.2:3 molar ratio).

[0163] The cells were cycled for one cycle at a charge / discharge rate of C / 24 at a temperature of 25°C for formation, then cycled at a rate of C / 10 for two more formation cycles, and finally cycled at a discharge rate of 1C and a charge rate of C / 3 for stability testing. + / Li 0 The voltages were set at 2 V and 4 V. Figure 12 compares the cycling stability of the resulting lithium foil with that of a lithium foil prepared by PVD.

[0164] Example 8: Electrodeposition of thin lithium films on treated copper foils in a membraneless electrochemical cell Electrodeposition of thin lithium films was carried out on different types of foils to improve lithium deposition.

[0165] The deposition was carried out using the same experimental setup as in Example 7 (cell without membrane, one rotating anode coated with LFP, and the same electrolyte formulation).

[0166] The electrochemical properties of each resulting lithium were compared with a commercially available lithium PVD cathode from Example 7. Figure 13 shows the cycling stability of each sample. The electrodeposited lithium performed better than or similar to the PVD lithium.

[0167] Example 8.1: Copper-silver substrate A cathode was prepared consisting of a 9 μm thick thin copper foil coated with a thin silver layer. The silver coating was prepared by cleaning the copper foil with acetone, immersing it in 1 M sulfuric acid at room temperature for 1 minute, rinsing the acid with water, and finally immersing the cleaned copper foil in an electroless silver plating solution for 10 seconds. The resulting treated current collector was dried before being used as a current collector in the membraneless cell described in Example 7. The current was 4 mA / cm. 2 for 22 minutes, and the active cathode surface area was 25.5 cm 2 The change in cell potential as a function of time is shown in Figure 14. The resulting electrodeposited lithium was washed and calendered using the same steps as in Example 7 before thickness measurement, which showed a lithium thickness of about 6.5 μm, and electrochemical cycling.

[0168] Example 8.2: Brass Foil Substrate Brass foil was used to demonstrate the lithophilicity of this alloy. This foil was a commercially available brass foil composed of 68% w / w copper and 32% w / w zinc. After being washed with acetone and properly dried, the 20 μm brass foil was used as the cathode in a lithium electrodeposition cell under conditions similar to those for the silver-plated copper foil described above. The change in cell potential as a function of time is shown in FIG. 15. The resulting electrodeposited lithium was washed and calendered using the same steps as in Example 7 before thickness measurements, which showed a lithium thickness of approximately 12 μm, and electrochemical cycling.

[0169] Example 8.3: 3D Textured Nickel Foil Substrate Electrodeposition of lithium was performed on commercially available textured nickel foil. This foil has a raised surface area due to 3D textured nickel dendrites. As in the previous examples, the 3D foil was used as the cathode substrate. Deposition was performed under the same conditions as for copper-silver or brass foils. The evolution of the cell potential as a function of time is shown in Figure 16. The resulting electrodeposited lithium was washed and calendered using the same steps as in Example 7 before thickness measurements, which showed a lithium thickness of approximately 9 μm.

[0170] Example 9: Electrodeposition of thin lithium on metallized polymers in a membraneless electrochemical cell Metallized polymers were used as electrodeposition substrates, and the results show that this substrate can be used successfully.

[0171] The metallized polymer consists of a 50 μm thick polyethylene terephthalate film coated with a thin copper film deposited by physical vapor deposition (PVD).

[0172] The electrodeposition of lithium was carried out in the same electrolyte as in Example 8.2, with the same structure as in Example 8.2. 2 A current density of was applied for 13 minutes.

[0173] The evolution of the cell potential as a function of time is shown in Figure 17. The resulting lithium foil is shown in Figure 18.

[0174] Example 10: Relithiation of the delithiated LFP anode of the above Tait cell A delithiated LFP (FP) electrode, produced by anodic discharge of LFP during the electrodeposition of lithium on a brass substrate as described in Example 8.2, was relithiated in aqueous LiHCO electrolyte. The relithiated electrode was then used to produce lithium. It was confirmed that the electrode was fully relithiated and successfully reused to produce lithium.

[0175] The initial LFP electrode used during lithium plating in Example 8.2 was a 25 cm 20 mm thick electrode coated with a mixture of LFP, conductive carbon, and PVDF as described in Example 7. 2 stainless steel disc with an active charge of 22.4 mg / cm 2 It was.

[0176] Considering the theoretical capacity of 170 mAh / g LFP, the LFP anode has a charge capacity of 97 mAh. The total electrodeposition charge was 36.7 mAh, which corresponds to approximately 38% delithiation of the LFP anode. The change in cell potential over time is shown in Figure 19.

[0177] This delithiated LFP electrode (referred to as the FP electrode) was recovered from the cell of Example 8.2, rinsed three times with THF and once with hexane, then dried and subsequently relithiated. The FP electrode was attached to a stirrer and immersed in a 0.5 M LiHCO solution at near-neutral pH. The electrolyte was prepared from ACS-grade lithium carbonate by dissolving the lithium salt in demineralized water in a pressurized reactor under 2 atmospheres of CO partial pressure. 25 cm 2 A platinum-plated titanium mesh was used as the anode. 4mA / cm 2 A constant current of 0.001 V was applied between the cathode and anode. The cathode potential was monitored with an Ag / AgCl reference electrode (3.5 M KCl at 0.198 V vs. NHE) immersed immediately next to the cathode. The current was stopped when the cathode potential fell below −0.5 V vs. NHE, indicating a high degree of lithiation (after 21 min).

[0178] The accumulated coulombic charge corresponds to 34.3 mAh. Figure 19 shows the current density and cathode potential as a function of time. The relithiation of the electrode was confirmed by FTIR, as shown in Figure 20. 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 pristine LFP, thereby confirming the complete relithiation of the electrode.

[0179] The previously relithiated LFP electrode was reused as the anode in a second electrodeposition of lithium. The electrochemical conditions were similar to those used in Example 7. The evolution of the cell potential, shown in Figure 21, is similar to that obtained in Example 8.2, confirming the feasibility of reusing the same LFP anode after the aqueous relithiation step.

[0180] Example 11: Relithiation of LTO anodes in aqueous solution This example shows the effect of the LTO electrode (Li4Ti5O 12 ) shows the relithiation of . Complete relithiation was confirmed.

[0181] LTO-based anodes, consisting of a thin layer of LTO coated on an aluminum / carbon foil, were electrochemically relithiated in an aqueous electrolyte. The electrolyte consisted of an aqueous solution of 25 M LiFSI with 25% v / v dimethoxyethane adjusted to pH 8 with 2 M LiOH. The working electrode was 4 cm 2 The LTO-coated foil was glued to a glass tile with aluminum foil on both sides. A square mask of PVDF tape was used to cover the edge of the working electrode, thereby forming a 3.5 cm square. 2 The active area of ​​the counter electrode is approximately 4 cm 2 It consisted of platinum mesh of 4mA / cm 2 A current of 0.01 V was applied between the cathode and anode for 60 minutes, and the potential of the working electrode was monitored with a platinum wire pseudo-reference electrode. The change in the potential of the working electrode is shown in FIG.

[0182] After relithiation, the working electrode was rinsed with ethanol and dried at 60 °C for several minutes. Relithiation was verified by performing linear sweep anodic voltammetry in the same electrolyte and using the same experimental setup. At this point, the potential of the working electrode was swept from 0 V vs. VCO to 1.2 V vs. the reference electrode at a sweep rate of 0.1 V / s. The resulting voltammetric curve, shown in Figure 23, is for Li4Ti5O 12 Li7Ti5O in 12 The figure shows a large oxidation peak centered at −0.357 V vs. Pt corresponding to the oxidation of

[0183] Example 12: Additives for thin lithium electrodeposition Additives can be added to the electrolyte to improve the appearance and properties of the lithium thin film. With this in mind, various additives that can improve the properties of lithium were tested. It was found that the use of these additives facilitates the electrodeposition of lithium.

[0184] The experiment consisted of the electrodeposition of lithium in a button cell using a 16 mm diameter, 4.5 μm thick copper foil as the cathode, covered with a 50 μm thick polypropylene mask with an inner diameter of 8 mm. Such a mask separates the two electrodes, creating a gap between the cathode and the membrane, simulating deposition in a membrane-less electrochemical cell. The anode consisted of an LFP film coated with aluminum foil, as shown in Example 7. The deposition was carried out at a current of 4 mA / cm. 2 The test was carried out for 10 minutes at a current density of 0.05.

[0185] A series of additives were added to a basic electrolyte consisting of 50 / 50 EC and DEC, with the concentrations of LiCF3COO and LiFSI electrolyte salts at 0.6 M and 0.4 M, respectively. As shown in Figure 24, the potential peak of the initial nucleation stage decreased after the addition of 0.2 M VC, 0.01 M LiDFOB, or 0.1 M CsPF6, which resulted in a more uniform coverage of the copper substrate surface during lithium electrodeposition.

[0186] Example 13: Synthesis of n-butyllithium from electrodeposited lithium The lithium obtained by electrodeposition was successfully used to synthesize n-butyllithium, a commonly used organometallic compound.

[0187] For this purpose, the initial electrodeposition was 1.44 mAh / cm on a 4.5 μm thick copper substrate. 2 0.5mA / cm for a total charge of 2 After electrodeposition, the resulting 16 mm diameter lithium electrodes were removed from the button cells in an argon-filled glove box, washed to remove electrolyte residue with THF and then DEC, and dried overnight in a drying chamber at 25 °C under vacuum.

[0188] To evaluate the efficiency of n-butyllithium formation, a titration curve was generated to accurately determine the concentration of n-butyllithium in n-hexane. Consequently, dilute solutions of n-butyllithium were prepared at four different concentrations (0.005 M / L, 0.01 M / L, 0.015 M / L, and 0.025 M / L) using a commercially available 1.6 M / L solution. 25 μl of a saturated solution of n-phenanthroline in a mixture of n-hexane and toluene was added to 2 ml of the previously prepared n-butyllithium solution. A diluted 2% v / v solution of 2-propanol in n-hexane served as the titrant and was added dropwise to a bright yellow endpoint. The volumetric concentrations of the titrant solution relative to the sample solution were plotted against the calculated concentrations of each dilute n-butyllithium solution, as shown in Figure 25. 2 A straight line was obtained with a 99.99% accuracy.

[0189] A diluted 2% v / v solution of n-butyl chloride was prepared in dried n-hexane to synthesize n-butyllithium from the electrodeposited lithium. A 14 mm diameter subsample was cut from the dried lithium electrode and placed in a vial. The charge on the lithium deposit was measured at 0.78 mg. A magnetic stirrer was placed in the vial containing 0.435 ml of the dilute butyl chloride solution. After the flask was sealed and stirred for 15 minutes, the solution was transferred to a 10 ml volumetric flask. The setup was rinsed three times with n-hexane and transferred to the volumetric flask to recover any traces of n-butyllithium from the vial and solid residue. After the gauge was filled with n-hexane, a 5 ml sample was taken from the volumetric flask and titrated for n-butyllithium with 2-propanol. For this purpose, 20 μl of saturated n-phenanthroline solution was added to the 5 ml. The resulting deep red color indicates the presence of n-butyllithium. The propanol solution was added dropwise to a bright yellow end point (0.070 ml in this case). The titration showed that 0.42 mg of lithium reacted with the butyl chloride, corresponding to a reaction efficiency of 67%.

[0190] Example 14: Prelithiation of Lithium Insertion Anodes The following examples demonstrate the application of the above electrochemical method to the prelithiation of lithium insertion anode materials with the aim of reducing the lithium losses induced during formation cycling. These lithium losses were largely offset in graphite and SiOx anodes after prelithiation.

[0191] In the first case, a commercially available graphite anode was used, made 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 and 2.27mAh / cm 2Coin cells comprising a 16 mm diameter electrode harvested from the graphite anode, a Celgard™ membrane, and a positive LFP electrode (as used in Example 12) were assembled for prelithiation. The electrolyte used corresponded to the base electrolyte of Example 12. These cells were then galvanostatically charged to drive the graphite electrode at 0.5 mA / cm. 2 The total charge was 0.36 mAh / cm 2 or 0.48mAh / cm 2 These coulombic charges correspond to 16% and 21% of the initial capacity of the graphite anode, respectively. The resulting galvanostatic curves are shown in Figure 26.

[0192] Similarly, 81% SiO x A commercially available silicon oxide anode was used, with a lithium intercalation layer composed of 4% carbon nanotubes and 15% polyimide. The total specific capacity of the anode was 2.52 mAh / cm. 2 The 16 mm diameter electrode was made of SiO2 for prelithiation of button batteries, as mentioned above. x The applied coulomb charge was 0.75 mAh / cm. 2 or 1.0mAh / cm 2 and SiO x These correspond to 30% and 40% of the total capacity of the anode. The galvanostatic curves obtained are shown in FIG.

[0193] The initial loss of capacity of each prelithiated anode was compared to the corresponding pristine anode by electrochemical cycling relative to the positive LFP electrode. The limiting potential galvanostatic cycling protocol began with a formation charge-discharge cycle at C / 24, followed by two additional formation cycles at C / 10, followed by a stability test at C / 3 charge and 1C discharge. The potential limits ranged from 2 V vs. lithium for graphite to 4 V vs. lithium for SiO xThe voltages were set from 2 V vs. lithium to 3.8 V vs. lithium for the anode. Figure 28 compares the cycling reversibility of the first formation cycle of the pristine graphite anode with that of the prelithiated graphite anode. The capacity loss of the pristine electrode reaches 21%, but at 15% capacity, the capacity loss of the prelithiated anode decreases to 3%. Meanwhile, at 20% capacity, the reversibility of the prelithiated anode is complete. Similarly, the SiO x Prelithiation of the anode improved the initial capacity loss from 68% for the pristine electrode to only 32% for the 30% prelithiated electrode and 11% for the 40% prelithiated electrode. x Cyclic reversibility of the first formation cycle of the anode and prelithiated SiO x Compare the cyclic reversibility of the first formation cycle of the anode.

[0194] The scope of the claims should not be limited by the preferred embodiments set forth in the examples, but should be accorded the broadest interpretation consistent with the description as a whole.

[0195] References This description makes reference to a number of documents, the contents of which are incorporated herein by reference in their entireties. These documents include, but are not limited to: ·Lee et al., “Synthesis of Lithium Thin Film by Electrodeposition from Ionic Liquid,” Applied Mechanics and Materials, 217-219, November 2012, pp 1049-1052 ·Porthault et al., “Electrodeposition of lithium metal thin films and its application in all-solid-state micro batteries,” Electrochimica Acta 194(2016)330-337 ·Coyle et al.,Recycle of End-of-Life NMC 111 Cathodes By Electrochemical Relithiation, 2019 Meet.Abstr.MA2019-02 449 ·Montoya et al.,Relithiation of Cathode Materials for the Recycling of Lithium-Ion Batteries,2019 Meet.Abstr.MA2019-02 444 ·Shi et al.,Ambient-Pressure Relithiation of Degraded LixNi 0.5 Co 0.2 Mn 0.3 O2(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·Zhou et al.,Direct recovery of scrapped LiFePO4 by a green and low-cost electrochemical re-lithiation method,Green Chem.,2022,24,6278-6286 ·Lahtinen et al.,Reuse of LiCoO2Electrodes Collected from Spent Li-Ion Batteries after Electrochemical Re-Lithiation of the Electrode,ChemSusChem 2021,14,1-12 ·Zhang et al.,Electrochemical Relithiation for Direct Regeneration of LiCoO2Materials from Spent Lithium-Ion Battery Electrodes, ACS Sustainable Chem.Eng.2020,8,31,11596-11605 ·Holtstiege et al.,Prelithiation Strategies for Rechargeable Energy Storage Technologies:Concepts,Promises and Challenges,Batteries 2018,4(1),4 ·WO2019 / 113534 ·WO2019 / 070896A1 ·WO2017 / 095989A1 ·WO2021 / 092692 ·US20220328800A1 ·US20210091426A1 ·US20210381115A1 ·US20180040914A1 ·US20160351889A1 ·CN112216819b ·CN110504451B ·EP3358046B1 ·DE102018207391A1

Claims

1. Relithiated lithium insertion materials for producing lithium metal or its alloys or for prelithiating electrode materials.

2. Use of the relithiated lithium insertion material to produce lithium metal or its alloys or to prelithiate electrode materials.

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

4. For prelithiating electrode materials, preferably for prelithiating anode materials, more preferably graphite, silicon, silicon oxide (SiO ｘ ), silicon-carbon composites, carbon nanotubes, or mixtures thereof.

5. The relithiated lithium insertion material is lithium phosphate or lithium oxide, preferably ・Li ｗ FePO ４ , Li ｗ Fe １－ｘ Mn ｘ P.O. ４ , Li ｗ Mn ２ O ４ , Li ｗ Mn １．５ Ni ０．５ O ４ , Li ４＋ｚ Ti ５ O １２ or NMC, and ｗ FePO ４ In the formula, w≦1.1, preferably w is 1; The formula Li ｗ Fe １－ｘ Mn ｘ P.O. ４ wherein w≦1.1, preferably w is 1, and x is in the range of 0<x≦1, preferably 0.2<x≦0.4; The formula Li ｗ Mn ２ O ４ In the formula, w≦1.1, preferably w is 1; The formula Li ｗ Mn １．５ Ni ０．５ O ４ In the formula, w≦1.1, preferably w is 1; The formula Li ４＋ｚ Ti ５ O １２ where z is in the range of 0<z≦3; The NMC is Li ｗ Ni １－ｘ－ｙ Mn ｘ Co ｙ O ２ 5. The material / use of any one of claims 1 to 4, wherein w≦1.3, preferably w is 1, x is in the range of 0≦x≦1, y is in the range of 0≦y≦1, z is in the range of 0≦z≦1, and M is aluminium, magnesium, titanium, niobium, zirconium, tungsten, molybdenum, yttrium, lanthanum, tantalum or mixtures thereof.

6. The relithiated lithium insertion material is Li ｗ FePO ４ 6. The material / use of claim 5, wherein:

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

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

9. A manufacturing anode for producing lithium metal or an alloy thereof or for prelithiating an electrode material, said manufacturing anode comprising a relithiated lithium insertion material.

10. Use of a manufacturing anode comprising a relithiated lithium insertion material to produce lithium metal or an alloy thereof or to prelithiate an electrode material.

11. 11. The manufacturing anode / use of claim 9 or 10, wherein the relithiated lithium insertion material is as defined in any one of claims 1 to 8.

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

13. 13. The manufacturing anode / use of claim 12, wherein the anode is intended for an electrolytic reaction to produce lithium.

14. 14. The manufacturing anode / use of claim 12 or 13, wherein the manufacturing anode further comprises a current collector, and the relithiated lithium insertion material is deposited on the current collector.

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

16. 16. The manufacturing anode / use of claim 14 or 15, wherein the current collector is coated with a primer, such as a carbon-containing paint.

17. 17. The manufacturing anode / use according to any one of claims 14 to 16, wherein the current collector is a current collector comprising a metal foil made from stainless steel or aluminium, preferably aluminium foil coated with carbon.

18. It is intended to prelithiate electrode materials, preferably anode materials, more preferably graphite, silicon, silicon oxide (SiO ｘ 12. The manufacturing anode / use according to any one of claims 9 to 11 for the purpose of prelithiating silicon-carbon composites, carbon nanotubes, or mixtures thereof.

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

20. 1. A manufacturing electrolytic cell for producing lithium metal or an alloy thereof or for prelithiating an electrode material, said manufacturing electrolytic cell comprising: a relithiated lithium insertion material used as a fabrication anode; a current collector or the electrode material used as a manufacturing cathode; a production electrolyte between the production cathode and the production anode, the production electrolyte comprising a production lithium salt dissolved in a production solvent.

21. 1. Use of a production electrolytic cell for producing lithium metal or an alloy thereof or for prelithiating an electrode material, said production electrolytic cell comprising: a relithiated lithium insertion material used as a fabrication anode; a current collector or the electrode material used as a manufacturing cathode; 1. Use of a manufacturing electrolytic cell comprising a manufacturing electrolyte between the manufacturing cathode and the manufacturing anode, the manufacturing electrolyte comprising a manufacturing lithium salt dissolved in a manufacturing solvent.

22. 22. The manufacturing electrolytic cell / use of claim 20 or 21, wherein the relithiated lithium insertion material is as defined in any one of claims 1 to 8.

23. A 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. 24. A manufacturing electrolytic cell / use according to any one of claims 20 to 23, for the production of said lithium metal or said alloy thereof, preferably for the production of said lithium metal, preferably said lithium metal or said alloy thereof in the form of a film, preferably said lithium metal or said alloy thereof being produced by electrodeposition, and wherein the current collector is used as a manufacturing cathode.

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

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

27. 27. A production electrolysis cell / use according to any one of claims 24 to 26, wherein the current collector used as the production cathode is made from one of copper, aluminium, protected aluminium, carbon, stainless steel, titanium, zinc, nickel, or alloys thereof, or is a metallised polymer-based current collector, or a mixture thereof.

28. A production electrolysis cell / use according to any one of claims 24 to 27, wherein the current collector used as the production cathode is made from passivated copper or aluminium.

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

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

31. 31. A manufacturing electrolysis cell / use according to any one of claims 24 to 30, wherein the surface of the current collector used as the manufacturing cathode is treated or modified to improve its lithophilicity.

32. 32. A manufacturing electrolysis cell / use according to any one of claims 24 to 31, wherein the surface of the current collector used as the manufacturing cathode is treated or modified to have a 3D structure, for example to improve the electrochemical performance or increase the reaction rate of the lithium layer in a battery when used in the preparation of an organolithium compound.

33. 33. The manufacturing electrolytic cell / use of any one of claims 24 to 32 for the production of said alloy, preferably said alloy comprising at least about 80% w / w lithium, more preferably at least about 85% w / w lithium, even more preferably at least about 90% w / w lithium, even more preferably at least about 95% w / w lithium, based on the total weight of the alloy.

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

35. The alloy salts include (fluorosulfonyl)(trifluoromethanesulfonyl)imide salts, 2-trifluoromethyl-4,5-dicyanoimidazolate (TDI) salts, 4,5-dicyano-1,2,3-triazolate (DCTA) salts, bis(pentafluoroethylsulfonyl)imide (BETI) salts, difluorophosphate (DFP), chloride salts, bromide salts, fluoride salts, hexafluoroarsenate (AsF ６ ), fluoroalkyl phosphate, tetrakis(trifluoroacetoxy)borate, bis(1,2-benzenediolato(2-)-O,O′)borate, difluoro(oxalato)borate, nitrate, trifluoroacetate, hexafluorophosphate, tetrafluoroborate, bis(oxalato)borate (BOB), perchlorate, bis(trifluoromethanesulfonyl)imide (TFSI) salt, bis(fluorosulfonyl)imide (FSI) salt, triflate salt, or a compound of formula BF ２ O ４ R ｘ － (R ｘ =C ２－４ 35. The manufacturing electrolysis cell / use of claim 34, wherein the salt has an anion having a hydroxyl group (alkyl).

36. 33. The production electrolytic cell / use of any one of claims 24 to 32, wherein the production electrolyte does not contain alloy salts and the production electrolytic cell / use is intended to produce lithium metal.

37. 24. A manufacturing electrolysis cell / use according to any one of claims 20 to 23, for prelithiating an electrode material, preferably for prelithiating an anode material, more preferably for prelithiating graphite, silicon, silicon oxide, or mixtures thereof, said electrode material being used as a manufacturing cathode.

38. The lithium salts used in the production include lithium (fluorosulfonyl) (trifluoromethanesulfonyl) imide, lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium difluorophosphate (LiDFP), lithium chloride (LiCl), lithium bromide (LiBr), and lithium hexafluoroarsenate (LiAsF ６ － ), lithium fluoroalkyl phosphate [LiPF ３ (CF ２ CF ３ ) ３ etc.], lithium tetrakis(trifluoroacetoxy)borate (LiB(OCOCF ３ ) ４ ), lithium bis(1,2-benzenediolato(2-)-O,O')borate (LiB(C ６ O ２ ) ２ ), lithium difluoro(oxalato)borate (LiBF ２ (C ２ O ４ )), formula BF ２ O ４ R ｘ － , LiCF ３ COO, LiF, LiNO ３ , LiPF ６ , LiBF ４ , LiBOB, LiClO ４ , LiTFSi, CF ３ SO ３ Li, LiFSi or any combination thereof, preferably of the formula LiCF ３ COO, LiF, LiNO ３ , LiPF ６ , LiBF ４ , LiBOB, LiClO ４ , LiTFSi, CF ３ SO ３ Li, LiFSi or any combination thereof, and having the formula BF ２ O ４ R ｘ － In R ｘ =C ２－４ The production electrolysis cell / use according to any one of claims 20 to 37, wherein the alkyl group is alkyl.

39. The lithium salt for production is CF ３ SO ３ 39. The manufacturing electrolysis cell / use of claim 38, wherein the Li is a combination of Li and LiFSi.

40. The production electrolyte further comprises one or more additives, preferably one or more additives that modify the morphology and / or properties of the lithium metal or said alloy thereof, one or more additives that affect the phase nucleation energy, one or more additives that affect the deposition potential of the lithium or said alloy thereof, and / or one or more additives that affect the electrodeposition efficiency of lithium, more preferably the additive(s) are / are: cyclic unsaturated carbonates such as vinylene carbonate (VC); halogenated cyclic carbonates such as fluoroethylene carbonate (FEC); nitrate, Lithium polymerization agents containing saturated or unsaturated hydrocarbon chains, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU); lithium passivation compounds, and / or 40. The manufacturing electrolysis cell / use of any one of claims 20 to 39, wherein the alkali salt of an organic acid is lithium difluoro(oxalato)borate (LiDFOB) or lithium oxalate.

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

42. 42. The manufacturing electrolytic cell / use of claim 41 , wherein the manufacturing 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, tetrafluoroethyl tetrafluoropropyl ether (TTE), tetraethylene glycol dimethyl ether (TEGDME), or any combination thereof.

43. 43. The manufacturing electrolytic cell / use of claim 42, wherein the manufacturing solvent is a combination of EC and DEC.

44. 44. A production electrolysis cell / use according to any one of claims 20 to 43, wherein the production electrolysis cell does not comprise a membrane separating the production anode from the production cathode.

45. 45. The manufacturing electrolysis cell / use of claim 44, wherein the manufacturing electrolysis cell is a roll-to-roll construction.

46. 46. ​​A manufacturing electrolytic cell / use according to claim 44 or 45, wherein the manufacturing electrolytic cell further comprises one or more calendering devices, for example pairs of spaced calender rolls.

47. 1. A method for producing lithium metal or an alloy thereof or for prelithiating an electrode material, said method comprising: a) providing a relithiated lithium insertion material; b) performing an electrolytic reaction for producing lithium in a production electrolytic cell, the production electrolytic cell comprising: the relithiated lithium insertion material as a fabrication anode; a current collector or the electrode material as a manufacturing cathode; a manufacturing electrolyte between the manufacturing cathode and the manufacturing anode, the manufacturing electrolyte including a manufacturing lithium salt dissolved in a manufacturing solvent; thereby allowing electrodeposition of lithium metal or an alloy thereof onto the current collector to be used as a manufacturing cathode or introducing lithium into the electrode material to produce a pre-lithiated electrode; thereby enabling the production of a partially or fully delithiated lithium insertion material.

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

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

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

51. 51. The method of any one of claims 47 to 50, wherein the electrolytic reaction to produce lithium is carried out by adjusting the cell potential between the production anode and the production cathode, or between the cathode and a reference electrode.

52. 51. The method of any one of claims 47 to 50, wherein the electrolytic reaction to produce lithium is carried out by adjusting the cell current.

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

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

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

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

57. The partially or fully delithiated lithium insertion material may be lithium phosphate or partially or fully delithiated lithium oxide, preferably partially or fully delithiated Li ｗ FePO ４ , Li ｗ Mn ２ O ４ , Li ４＋ｚ Ti ５ O １２ , or NMC (Li ｗ Ni １－ｘ－ｙ Mn ｘ Co ｙ M ｚ O ２ 57. The method according to any one of claims 47 to 56, wherein

58. The partially or fully delithiated lithium insertion material may be a partially or fully delithiated Li ｗ FePO ４ 58. The method of claim 57, wherein:

59. 59. A method according to any one of claims 47 to 58, wherein the relithiated lithium insertion material is washed, preferably washed and dried, before being used in step b).

60. Step a) comprises: a') providing a partially or completely delithiated lithium insertion material; a'') relithiating the partially or fully delithiated lithium insertion material to allow for the production of a relithiated lithium insertion material.

61. 61. The method of claim 60, further comprising step c) repeating steps a) and b) one or more times using the partially or fully delithiated lithium insertion material produced in step b) in step a′) and step a″).

62. 62. The method of claim 60 or 61, wherein the partially or fully delithiated lithium insertion material provided in step a′) is the partially or fully delithiated lithium insertion material produced in step b).

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

64. Step a″) comprises conducting an electrolytic relithiation reaction in an electrolytic relithiation cell, said electrolytic relithiation cell comprising: the partially or fully delithiated intercalation material as a relithiated cathode; a relithiated anode; and a relithiated electrolyte between the relithiated cathode and the relithiated anode, the relithiated electrolyte comprising a relithiated lithium salt dissolved in a relithiated solvent; 64. The method of any one of claims 47 to 63, thereby enabling relithiation of the partially or fully delithiated insertion material and production of the relithiated lithium insertion material.

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

66. 66. The method of claim 64 or 65, wherein the relithiated anode is made from a material compatible with the anode reaction occurring at the relithiated anode, preferably a material compatible with the oxygen releasing reaction.

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

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

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

70. The relithiated salt is Li ２ CO ３ , LiHCO ３ , LiOH, LiNO ３ , LiOH, Li ２ SO ４ , LiCH ３ COO, LiFSI, LiTFSI, Li ２ C ２ O ４ or a mixture thereof, preferably the relithiated salt is LiHCO ３ , Li ２ SO ４ or a mixture thereof, more preferably the relithiated salt is Li ２ SO ４ The method according to any one of claims 64 to 69, wherein

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

72. 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 relithiated salt is LiHCO ３ 73. The method of any one of claims 64 to 72, wherein the compound is a water-soluble relithiated salt having a water solubility greater than that of the compound of formula (I).

74. LiHCO ３ The water-soluble relithiated salt having a water solubility greater than that of LiNO ３ , Li ２ SO ４ , or LiCH ３ 74. The method of claim 73, wherein the COO.

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

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

77. 77. The method of claim 76, wherein the lithium precursor and the reagent are added to a salt-forming compartment of the electrolytic relithiation cell that is in fluid communication with a main compartment of the electrolytic relithiation cell, the main compartment comprising the relithiated cathode and the relithiated anode.

78. 75. 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. 80. The method of claim 78, further comprising reacting a lithium precursor with a reagent in a reactor separate from the electrolytic relithiation cell to obtain the relithiated salt, and thereafter adding the relithiated salt to the electrolytic relithiation cell.

80. The lithium precursor is Li ２ CO ３ , LiOH or mixtures thereof, preferably Li ２ CO ３ 80. The method of any one of claims 76, 77 and 79, wherein

81. The reagent is CO ２ , H ２ SO ４ , nitric acid, acetic acid, oxalic acid, or the acid form of a sulfonylimide salt, or a mixture thereof, preferably CO ２ Or H ２ SO ４ 81. The method of any one of claims 76, 77, 79 and 80, wherein the compound is a hydroxybenzoate or a mixture thereof.

82. The reagent is CO ２ 82. The method of claim 81, wherein:

83. The reagent is H ２ SO ４ 82. The method of claim 81, wherein:

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

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

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

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

88. 64. The method of any one of claims 47 to 63, wherein step a'') comprises: (i) adding the partially or fully delithiated insertion material to a solution comprising a reducing agent and a relithiation salt in a solvent to allow for the relithiation of the partially or fully delithiated insertion material and the production of the relithiated lithium insertion material.

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

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

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

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

93. 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)] ＋ 93. The method of claim 92, wherein the cation is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29,

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

95. 95. The method of any one of claims 88 to 94, wherein step (i) and / or step (iii) is carried out in the absence of oxygen.

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

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

98. 98. A method according to any one of claims 88 to 97, wherein step (iii) is carried out in an electrolysis cell by passing an electric current between at least one cathode and at least one anode.

99. 99. The method of claim 98, wherein the electrolysis cell includes at least one ionic or non-ionic separator mounted between the anode and the cathode to protect the regenerated reducing agent.

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

101. 101. A method according to any one of claims 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. A method according to any one of claims 98 to 100, wherein step (iii) is carried out by adjusting the cell current.

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

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

105. 105. The method of any one of claims 47-104, 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. 106. The method of any one of claims 47 to 105, further comprising using the current collector with the lithium metal or 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 alloy thereof for pre-lithiating an electrode material, or as a source of lithium metal or alloy thereof for manufacturing an energy storage system.

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

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

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

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

111. 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. 111. The method of claim 110, further comprising transferring the current collector with the lithium metal or the alloy thereof produced in step b) to another reactor, preferably in a roll-to-roll mode, and reacting the lithium metal or the alloy thereof with reactants in the other reactor to produce the organolithium compound.

113. It is intended to prelithiate electrode materials, preferably anode materials, more preferably graphite, silicon, silicon oxide (SiO ｘ ), silicon-carbon composite, carbon nanotubes, or mixtures thereof, and the electrode material is used as a manufacturing cathode.

114. 113. The method of any one of claims 47 to 112, for producing said lithium metal or said alloy thereof, preferably for producing said lithium metal, preferably said lithium metal or said alloy thereof is produced by electrodeposition, and said current collector is used as a production cathode.

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

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

117. 117. A lithium battery comprising the lithium electrode of claim 116, preferably the battery being a lithium ion battery or an all-solid-state battery.

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