WO2021119310A1

WO2021119310A1 - Pre-lithiated electrode

Info

Publication number: WO2021119310A1
Application number: PCT/US2020/064308
Authority: WO
Inventors: Jack W. Marple; Robert E. PACA; Naba K. KARAN; Vedasri Vedharathinam
Original assignee: Alpha-En Corporation
Priority date: 2019-12-10
Filing date: 2020-12-10
Publication date: 2021-06-17

Abstract

A pre-lithiated electrode that has not undergone a charge cycle and contains high purity lithium is obtained by electrodeposition of lithium onto an electrode using a selective lithium ion conducting layer. The electrodeposition process can provide lithium intercalated into or plated onto the electrode. The pre-lithiated electrode advantageously offsets the loss of lithium capacity that occurs during the first charge/discharge cycle in a lithium ion battery.

Description

PRE-LITHIATED ELECTRODE

[0001] The present disclosure relates to pre-lithiated electrodes that have not undergone a charge cycle and to methods of preparing the pre-lithiated electrodes, such as pre-lithiated cathodes or pre-lithiated anodes, using a selective lithium ion conducting layer or membrane to obtain lithium intercalated into or plated on the electrode. The method enhances the lithium content of pre-lithiated electrodes that may advantageously offset the loss of lithium capacity that occurs during the first charge/discharge cycle in a lithium ion battery

BACKGROUND

[0002] Lithium-ion cells are typically made from electrode materials in their discharged states, with all the lithium available for cycling in the cell originating from the cathode active material. When the cell is charged for the first time, all the lithium that can be extracted from the cathode (or positive electrode) by electrochemical oxidation is transferred to the anode (or the negative electrode). However, the initial reductive electrochemical processes undergone by low potential, high energy lithium-ion anode materials used in high-energy lithium-ion cells are not entirely reversible. Irreversible electrolyte reduction processes consume both charge and active lithium to form passivating films on the anode surface, known as solid electrolyte interphase (SEI), that prevent further reduction of the electrolyte. The charge and cyclable lithium lost to these passivation processes directly diminish the cell’s cycling capacity, and thus its energy density. This may be referred to as initial capacity loss or irreversible capacity loss, and typically amounts to a loss in capacity of 7 to 12 percent for typical graphite anodes.

[0003] One possible solution to compensate for active lithium losses and to increase the practical energy density is to pre-lithiate the electrodes. Pre- lithiation refers to the addition of lithium to the active lithium content of a lithium ion battery prior to battery cell operation. Pre-lithiation allows for a lithium content greater than that defined by stoichiometric cathode limitations and can be utilized to offset irreversible loss of active lithium during electrode passivation associated with wasteful reactions with organic electrolytes. [0004] One possible drawback to currently existing methods of pre- lithiating electrodes is that they add process steps and increase manufacturing complexity and costs. Further, pre-lithiating electrodes may impact product safety and/or reduce the uniformity of the lithium within the cell construction. There is therefore a need for uniformly pre-lithiated electrodes that offset the loss of lithium capacity that occurs during the first charge/discharge cycle. Further, there is a need for efficient methods of obtaining pre-lithiated electrodes.

SUMMARY

[0005] Aspects and embodiments of the present invention are set out in the appended claims. These and other aspects and embodiments of the invention are also described herein.

[0006] Pre-lithiated electrodes that have not undergone a charge cycle, and methods of preparing the pre-lithiated electrodes are described. The pre- lithiated electrodes may contain high purity lithium.

[0007] In an embodiment of the present disclosure, which may be combined with any other embodiment unless specified otherwise, a pre- lithiated electrode that has not undergone a charge cycle is provided. The pre- lithiated electrode may be obtained by electrodeposition of lithium within an electrode using a selective lithium ion conducting layer or membrane. It is to be noted that, as used in the following description, reference to “the selective lithium ion conducting layer” also refers to a selective lithium ion conducting membrane or structure, even if such is not specifically recited, unless otherwise noted.

[0008] In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, the pre-lithiated electrode comprises lithium intercalated within or plated on the electrode.

[0009] In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, the selective lithium ion conducting layer or membrane comprises an active metal ion conducting glass or glass-ceramic. [0010] In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, the selective lithium ion conducting layer or membrane comprises a lithium ion conductive barrier film.

[0011] In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, the pre-lithiated electrode is obtained by extracting the lithium from a lithium salt using the selective lithium ion conducting layer or membrane.

[0012] In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, the pre-lithiated electrode may contain a solid electrolyte interphase layer.

[0013] In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, the lithium transported through the conducting layer is free of metal impurities.

[0014] In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, the lithium is free of at least one impurity selected from the group consisting of mercury, boron, sodium, aluminum, potassium, calcium, chromium, manganese, and nickel.

[0015] In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, the lithium is free of mercury.

[0016] In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, the lithium is free of other metals except those which are a deliberate product of a controlled solid electrolyte interphase layer.

[0017] In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, the lithium deposited has a purity of greater than 99.96 weight percent basis on a metal basis. [0018] In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, the lithium has a purity of at least 99.99 weight percent on a metal basis.

[0019] In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, the lithium has a purity of at least 99.998 weight percent on a metal basis.

[0020] In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, the pre-lithiated electrode is a cathode or an anode.

[0021] The anode may include lithium-graphite intercalation compounds, lithium-silicon alloys, Si-based alloys such as SiOx, Al, Sn, Ge, or any combination thereof, lithium-tin compounds, and other lithium alloys. The anode may optionally include electrically conductive material such as carbon black, graphite, carbon nanotubes, carbon fibers, nitrogen-doped carbon, and combinations thereof. The anode may also be a carbon anode that may also include Sn or Si as the primary or secondary intercalation component.

[0022] In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, the anode is a copper current collector. In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, the anode is a graphite-based current collector.

[0023] The cathode may include electrochemically active materials such as: lithium cobalt dioxide, lithium nickel-manganese-cobalt (NMC) oxides in any ratio of these metals, lithium iron phosphate, lithium nickel oxide, lithium manganese spinel, lithium vanadium oxide, as well as other lithium based electrochemically active cathode materials and combinations thereof.

[0024] In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, a battery including a cathode and an anode is provided, wherein at least one of the cathode or the anode is pre-lithiated, has not undergone a charge cycle, and was obtained by electrodeposition of lithium onto an electrode using a selective lithium ion conducting layer. The electrodeposited lithium may be intercalated within the electrode or may be plated onto the electrode. In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, the battery is selected from the group consisting of a lithium primary battery, a rechargeable lithium metal battery, a rechargeable lithium-ion battery, a thin film lithium-ion battery, a lithium-ion polymer battery, a lithium iron phosphate battery, a lithium sulfur battery, a solid-state lithium battery, a lithium air battery, and a nanowire battery. In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, the lithium transported through the conductive layer and deposited within the battery electrode is free of metal impurities.

[0025] In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, the battery comprises recycled battery materials.

[0026] In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, a method of pre-lithiating an electrode is provided. The method may include electrodepositing lithium onto or within the electrode using a selective lithium ion conducting layer. In an embodiment of the present disclosure, which may be combined with any other embodiment listed herein unless specified otherwise, the method comprises extracting lithium from a lithium salt using the selective lithium ion conducting layer.

[0027] One advantage of the present disclosure is to provide high purity pre-lithiated electrodes that offset the loss of lithium capacity that occurs during the first charge/discharge cycle. The pre-lithiated electrode is obtained using a selective lithium ion conducting layer or membrane as a means of electrodepositing lithium beyond the base design of the electro-active components.

[0028] Another advantage of the present disclosure is to increase the energy density of lithium ion cells.

[0029] Another advantage of the present disclosure is to provide an efficient, simple method for preparing high purity pre-lithiated electrodes using a selective lithium ion conducting layer and which may include the use of low- cost aqueous salts as a lithium source feedstock.

[0030] Another advantage of the present disclosure is to pre-wet the electrodes with electrolyte as they pass through the plating bath, reducing a production bottleneck associated with incorporating electrolyte into the electrodes as well as enhancing the uniformity of electrolyte within the electrode structure.

[0031] Another advantage of the present disclosure is that it provides a pathway for the use of recycled battery components which are partially lithium depleted.

[0032] Other advantages of the present disclosure include improving the consistency of ion transfer and the electrochemical battery reactions, and improving cycle life.

[0033] The invention extends to methods, systems, kits of parts and apparatus substantially as described herein and/or as illustrated with reference to the accompanying figures.

[0034] The invention extends to any novel aspects or features described and/or illustrated herein. In addition, apparatus aspects may be applied to method aspects, and vice versa. Furthermore, any, some and/or all features in one aspect can be applied to any, some and/or all features in any other aspect, in any appropriate combination.

[0035] It should also be appreciated that particular combinations of the various features described and defined in any aspects of the invention can be implemented and/or supplied and/or used independently.

[0036] Unless otherwise explicitly noted, all percentages in the disclosure refer to a percent by weight. It should also be noted that reference to lithium refers to elemental lithium unless the reference or context makes clear that it refers to lithium ion. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] The following description accompanies the drawings, all given by way of non-limiting examples that may be useful to understand the described pre-lithiated electrodes and methods for making the pre-lithiated electrodes. [0038] FIG. 1 shows a schematic elevation view of a lithium producing cell structure that may be useful for pre-lithiating an electrode.

[0039] FIG. 2 shows a schematic detail of the lithium producing cell structure of FIG. 1.

[0040] FIG. 3 shows a schematic exploded detail of another lithium producing cell that may be useful for pre-lithiating an electrode.

[0041] FIG. 4 shows a perspective view of another embodiment of a lithium producing cell that may be useful for pre-lithiating an electrode.

[0042] FIG. 5 shows a perspective view of the lithium producing cell from the side opposite that shown in FIG. 4.

[0043] FIG. 6 is an exploded view of the lithium producing cell of FIG. 4. [0044] FIG. 7 shows the cycling performance in terms of discharge capacity up to 100 cycles of a pre-lithiated graphite anode electrode according to the description in comparison to a non-pre-lithiated graphite anode electrode. Both of the underlying commercial electrodes were obtained from the same source, source 1 for this example.

[0045] FIG. 8 shows the cycling performance in terms of discharge capacity variation as a function of cycle number of two types of coin cells, one using non-pre-lithiated graphite anode and other using 10% pre-lithiated graphite anode. Both of the underlying commercial electrodes were obtained from the same source, source A for this example.

[0046] FIG. 9 shows the cycling performance of two types of coin cells, one using non-pre-lithiated graphite anode and other using 10% pre-lithiated graphite anode. Both of the underlying electrodes were from the same source, source B.

[0047] FIG. 10 shows the 50th discharge capacity for pre-lithiated anodes where the underlying electrodes were from the same source.

[0048] FIG. 11 shows the 50th discharge capacity for pre-lithiated anodes where the underlying electrodes were from the same source, which differed from the source of the underlying electrodes shown in FIG. 10. [0049] FIG. 12 shows the cycling performance in terms of discharge capacity variation as a function of cycle number of two types of coin cells, one using a non-pre-lithiated Si-based anode and other using pre-lithiated Si- based anode. Both of the underlying commercial Si-based electrodes were obtained from the same source.

DESCRIPTION

[0050] A method of making pre-lithiated electrodes may include an electrolytic process that continuously produces lithium from lithium carbonate or other lithium salts that dissociate in an acid electrolyte and release the non lithium portion of the feed stock as gas. Such a method is described in U.S. Patent Publication No. 2015/0014184 to Swonger, the contents of which are incorporated herein by reference. In this process, an aqueous acid electrolyte and a lithium producing cell structure continuously produce lithium from the lithium salt. The lithium producing cell structure includes a cell body, a cathode, an aqueous electrolyte solution containing lithium ion and an anion, and a composite structure, layer, or membrane intercalated between the cathode and the electrolyte aqueous solution. The composite layer or membrane comprises a lithium ion conductive glass ceramic (LIC-GC) and may also comprise a lithium ion conductive barrier film (LI-BF) that isolates cathode-forming lithium from the electrolyte aqueous solution. The LIC-GC-BF composite allows for direct production of lithium from solution and direct deposition of lithium onto a clean cathode, without the need for an additional extraction process.

[0051] Turning now to FIGs. 1 and 2, FIG. 1 shows a schematic elevation view of a lithium producing cell structure, and FIG. 2 shows a schematic detail of the cell structure of FIG. 1. With the apparatus shown in FIGs. 1 and 2, lithium-rich electrolyte flows through an extraction cell. When a potential is applied to the system, lithium builds up on a moving cathode below an intercalated composite layer.

[0052] As shown in FIGs. 1 and 2, the electrolytic cell 10 includes an upper section 12 and a lower section 14. The cell 10 includes a movable cathode 16 that transects a cross-section of the cell. The cathode 16 transposes an axis of cell 10, advancing as an electrolysis reaction takes place in electrolyte 18 above the cathode 16, through the LIC-GC-BF composite layer or membrane. Anode 20 is provided to the cell upper section 12. The cell section 12 above the cathode 16 is loaded with electrolyte 18 via inlet 22, electrolysis proceeds and spent electrolyte is discharged via outlet 24. The cathode 16 is in contact with the electrolyte 18 through a composite layer or membrane 28 intercalated between the cathode 16 and electrolyte 18. The composite layer or membrane 28 comprises a lithium ion conductive glass ceramic layer (LI-GC) 30 adjacent the electrolyte 18 and a lithium ion conductive barrier film (LI-BF) 32 interposed between the ceramic layer 30 and the cathode 16. The composite membrane 28 comprising a barrier layer, membrane, or structure 32 and a glass ceramic layer, membrane, or structure 30 isolates lithium forming at the cathode 16 from the electrolyte 18. The shaft 26 advances the cathode 16 and the composite layer or membrane 28 as lithium is formed and deposited through the composite layer or membrane 28 onto the advancing cathode 16. The lithium produced at the solid cathode 16 can be drawn off as pure lithium.

[0053] Suitable electrolyte 18 components include water-soluble lithium salts including but not limited to U2CO3 and LiCI. To improve solubility, the lithium salts may be dissolved in hydrated acid such as sulfuric acid and used as the electrolyte 18 in the electrolytic cell 10. Lithium carbonate (U2CO3) is a readily available lithium salt and was used as feed stock for initial trials of the cell 10.

[0054] The use of sulfuric acid may be important for efficient production of lithium from lithium carbonate because lithium carbonate is essentially insoluble in water and organic solvents, whereas lithium carbonate has a much higher solubility in a sulfuric acid solution. By disassociating the lithium carbonate and only placing the lithium ions into solution, the electrolyte solution remains stable and does not build up a concentration of the nonlithium ion portion of the feed stock. Lithium carbonate can be continuously fed into a tank outside of the electrolysis cell, venting off the CO2 gas released by the sulfuric acid electrolyte and harvesting lithium from a cathode. This can be continuously operated or conducted as a batch process. [0055] Some suitable components for the electrolytic cell 10 are described in U.S. Patent Publication No. 2013/0004852 A1 , the entire contents of which is incorporated herein by reference.

[0056] The pre-lithiated cathode 16 may be characterized by an intercalated composite (Li-GC/Li-BF) layer 28, which means that the composite layer 28 is located, inserted, or interposed between the cathode 16 and the electrolyte 18. The cathode 16 advances along an axis of the cell 10 to transpire produced lithium through the composite 28 and to isolate cathode- deposited lithium. The cathode 16 comprises a suitable material that is non reactive with lithium (or lithium metal) and the composite layer. The Li-GC/Li- BF composite layer or membrane 28 is a stationary barrier structure located between the anode compartment and the lithium forming on the cathode. The cathode 16 moves to accommodate the continuously thickening layer of lithium on the cathode 16.

[0057] The composite layer, structure, or membrane (Li-GC/Li-BF) 28 includes a selective lithium ion conductive glass ceramic layer, structure or membrane (LI-GC) 30 and lithium ion conductive barrier film (LI-BF) 32. The substantially impervious layer, structure, or membrane (LI-GC) 30 can be an active metal ion conducting glass or glass-ceramic (e.g., a lithium ion conductive glass-ceramic that has high active metal ion conductivity and stability to aggressive electrolytes that vigorously react with lithium metal. Suitable materials are substantially impervious, ionically conductive and chemically compatible with aqueous electrolytes or other electrolyte (catholyte) and/or cathode materials that would otherwise adversely react with lithium metal. Such glass or glass-ceramic materials are substantially gap- free, non-swellable and do not depend on the presence of a liquid electrolyte or other agent for their ionically conductive properties. They also have high ionic conductivity, at least 10⁷ S/cm, generally at least 10⁶ S/cm, for example at least 10⁵ S/cm to 10 S/cm, and as high as 10^-3 S/cm or higher so that the overall ionic conductivity of the multi-layer protective structure is at least 10⁷ S/cm and as high as 10³ S/cm or higher. The thickness of the layer, structure, or membrane is about 0.1 to 1000 microns, or, where the ionic conductivity of the layer is about 10⁷ S/cm, about 0.25 to 1 micron, or, where the ionic conductivity of the layer is between about 10⁴ and about 10³ S/cm, or about 10 to 1000 microns, or between 1 and 500 microns, or between 50 and 250 microns, and, in one instance about 150 microns.

[0058] Examples of the glass ceramic layer, structure, or membrane (LiC- GC) 30 include glassy or amorphous metal ion conductors, such as a phosphorus-based glass, oxide-based glass, phosphorus-oxynitride-based glass, sulfur-based glass, oxide/sulfide based glass, selenide based glass, gallium based glass, germanium-based glass or boracite glass (such as are described D. P. Button et al., Solid State Ionics, Vols. 9-10, Part 1 , 585-592 (December 1983)); ceramic active metal ion conductors, such as lithium beta- alumina, sodium beta-alumina, Li superionic conductor (LISICON), Na superionic conductor (NASICON), and the like; or glass ceramic active metal ion conductors. Specific examples include LiPON, LbPC , U2S, S1S2, U2S, GeS2, Ga2S3 and U2O.

[0059] Suitable LiC-GC materials include a lithium ion conductive glass- ceramic having the following composition in mol percent: P2O5 26-55%; S1O2 0-15%; Ge0₂+Ti0₂25-50%; in which Ge0₂ 0-50%; T1O20-50%; Zr0₂ 0-10%; M2O3 0-10%; AI2O30-15%; Ga203 0-15%; Li203-25% and containing a predominant crystalline phase comprising Lii_+X(M, Al, Ga)x(Gei-_yTi_y)2-x(P04)3 where X < 0.8 and 0 £ Y £ 1 .0 and where M is an element selected from the group consisting of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb, and/or Lii_+x+yQxTi2-xSi3P3-_yOi2 where 0 < X < 0.4 and 0 < Y < 0.6, and where Q is Al or Ga. Other examples include HAI2O3, Na20nAl203, (Na, U)i_+xTi2-xAlx(P04)3 (0.6 < x < 0.9) and crystallographically related structures, Na3Zr2Si2POi2, Li3Zr2Si2P04, NasZrP30i2, NasTiP30i2, Na3Fe2P30i2, Na4NbP30i2,

Li5ZrP30i2, Li5TiP30i2, LisFe2P30i2 and LUNbP30i2 and combinations thereof, optionally sintered or melted. Suitable ceramic ion active metal ion conductors are described, for example, in U.S. Pat. No. 4,985,317 to Adachi et al. incorporated herein by reference.

[0060] Suitable LiC-GC materials also include a product from Ohara, Inc. (Kanagawa, JP), trademarked LIC-GC™, LISICON, L^O-A^Os-SiO^Os- T1O2 (LATP), and other materials with similarly high lithium ion conductivity and environmental/chemical resistance such as those manufactured by Ohara and others such as described in U.S. Pat. No. 8,476,174, the contents of which are incorporated herein by reference. Other suitable glass-ceramics include crystallines having a having a ϋTΪ2R3qΐ2 structure, the crystallines satisfying 1< IAH3/IAIO4 < 2, wherein IAIO4 is the peak intensity assigned to the plane index 104 (20=20 to 21°), and IAH3 is the peak intensity assigned to the plane index 113 (20=24 to 25°) as determined by X-ray diffractometry.

[0061] The lithium ion conductive barrier film 32 (Li-BF) may be a lithium ion conductive film or coating with high lithium ion conductivity, typically 1 .0 mS/cm to 100 mS/cm. A high lithium ion transference number (t₊) is desired. Low t₊Li⁺ electrolytes will hinder performance by allowing ion concentration gradients within the cell, leading to high internal resistances that may limit cell lifetime and limit reduction rates. Transference numbers between t₊=0.70 and t₊ = 1 .0 are desirable. The lithium ion conductive barrier film is non-reactive to both lithium and the LI-GC material.

[0062] The LI-BF film 32 may include an active metal composite, where the "active metal” may be lithium, sodium, magnesium, calcium, and aluminum used as the active material of batteries. Suitable materials forming the LI-BF film may include a composite reaction product of an active metal with Cu3N, active metal nitrides, active metal phosphides, active metal halides, active metal phosphorus sulfide glass and active metal phosphorous oxynitride glass (CusN, L₃N, LisP, Lil, LiF, LiBr, LiCI and UPON). U.S. Patent Publication No. 2015/0014184 teaches that the LI-BF material should also protect against dendrites that may form on the cathode from coming in contact with the LI-GC material. This may be accomplished by creating a physical distance between the cathode and LI-GC and/or by providing a physical barrier that the dendrites do not penetrate easily. One type of LI-BF film is a physical organogel electrolyte produced by in situ thermo-irreversible gelation and single ion-predominant conduction as described by Kim et al. in Scientific Reports (article number: 1917 doi : 10.1038/srep01917). This electrolyte has t₊=0.84 and conductivity of 8.63 mS/cm at room temperature. This organogel electrolyte can be set up in a porous membrane to provide additional structure and resistance to dendrite penetration. Typical porous membrane thickness is 1 urn to 500 urn, for example 20 urn. Acceptable porous membrane includes HIPORE polyolefin flat-film membrane by Asahi Kasei E-materials Corporation. [0063] The described continuous lithium production process can utilize inexpensive lithium carbonate or an equivalent source of lithium ions to produce lithium metal directly from the acid solution used to leech lithium metal out of spodumene ore or other natural lithium sources.

[0064] An exemplary process for pre-lithiating electrodes may use the cell shown schematically in FIG. 3. The cell 110 includes cell cover 116, retainer 118, Pt anode 112, cathode 124 and a LiC-GC conductive glass 114 with lithium ion conductive barrier film 120 incorporated into a porous polyolefin flat-film membrane 122. The supported LiC-GC-BF multilayer membrane or structure is intercalated between the cathode 124 and a lithium ion-rich electrolyte 18 (as shown in Figures 1 and 2). The cell further comprises a supporting Teflon® sleeve structure 126 with gaskets 128. One gasket seals between the LiC-GC and the housing to prevent leakage of the electrolyte from the anode compartment into the cathode compartment. The other gasket allows for even compression of the LiC-GC by the Teflon sleeve to prevent breakage of the LiC-GC plate.

[0065] The cell 110 includes an anode 1 12 that is a platinized titanium anode, Gc4” rhodium and palladium jewelry plating. The cathode is a palladium cathode disc fabricated in-house, 1 .4 inch round. The LiC-GC 114 material is LICGC® G71 -3 N33: DIA 2 INx 150 pm tape cast, 150 pm thick, 2 inch round from Ohara Corporation, 23141 Arroyo Vista, Rancho Santa Margarita, California 92688.

[0066] The lithium ion conducting gel electrolyte 120 is fabricated from: a PVA-CN polymer supplied by the Ulsan National Institute of Science and Technology in Ulsan South Korea, Dr. Hyun-Kon Song, procured from Alfa Aesar, stock number H61502; LiPFe (lithium hexafluorophosphate), 98%;

EMC (ethyl methyl carbonate), 99%, from Sigma Aldrich, product number 754935; EC (ethylene carbonate), anhydrous, from Sigma Aldrich, product number 676802; and a porous membrane, ND420 polyolefin flat-film membrane from Asahi Corp.

[0067] The Li-BF barrier layer 120 is fabricated in an argon purged glove bag. The glove bag is loaded with all materials, precision scale, syringes, and other cell components then filled and evacuated four times before the start of the electrolyte fabrication process. [0068] The organogel electrolyte is mixed as follows: 4.0 ml of EMC is liquefied by heating to about 140° F and placed in a vial. 2.0 ml of the EMC is then added-to the vial, 0.133 g (2% wt) PVA-CN polymer is added to the vial and the mixture is agitated for 1 hour to dissolve the PVA-CN. Then 0.133 g (2% wt) FEC is added as SEI-forming additive, 0.972 g (1 M) LiPF6 is then added and mixed to complete the organogel electrolyte mixture. The electrolysis cell is then assembled inside the glove bag. With the LiC-GC and gaskets in place, the anode and cathode compartments are sealed from each other. The organogel electrolyte mixture is used to wet the cathode side of the LiC-GC, the HIPORE membrane is placed on the cathode side of the LiC-GC and wetted again with organogel electrolyte mixture. The cathode disc is then placed on top of the organogel mixture. The cell is placed in a Mylar® bag and sealed while still under argon purge. The sealed Mylar® bag with assembled cell is then placed in an oven at 60° C for 24 hours to gel the electrolyte.

[0069] The electrolysis cell 110 is removed from the oven and placed in the argon purged glove bag, and allowed to cool to room temperature. Clear polypro tape is used to seal the empty space above the cathode disc and secure the electrode wire. The electrolysis cell 110 is now ready for use, is removed from the glove bag, and is connected to the electrolyte circulating system.

[0070] An electrolyte 18 is prepared with 120 g of lithium carbonated in 200 ml of deionized water and 500 ml of 20% wt sulfuric acid. The sulfuric acid is slowly added to the lithium carbonate suspension and mixed well. Undissolved lithium carbonate is allowed to settle. A supernatant is collected from the stock solution, an 18% wt lithium stock solution. The 18% wt lithium solution has a measured pH of 9. Solution pH is lowered by addition of 20% wt sulfuric acid. Again, the sulfuric acid is added slowly to minimize foaming. The 18% wt lithium stock solution is adjusted to pH 4.5 or a pH between pH 3.0 and pH 4.5, or between pH 3 .0 and pH 4.0, but the process can be run at a pH of 7.0 or below. A pH above 7.0 will result in carbonate in solution.

[0071] The electrolyte mixture is then poured into the circulating system. A circulating pump (not shown) is primed and solution circulated for 30 minutes to check for leaks. [0072] The lithium ion-rich electrolyte 18 flows through the top half of the cell 110 over the LiC-GC-BF multilayer 114/120 and past the anode 112. When a potential is applied to the system, lithium builds up on the moving cathode below the LiC-GC-BF multilayer 114/120 system.

[0073] A Gamry Reference 3000 Potentiostat/Galvanostat/ZRA is attached to the cell 110. At voltages of -3 to -6 volts there is no significant activity. When the voltage is raised to -10V, the system responds. Amperage draw increases when the voltage is raised to 11 vdc. No gassing on the anode side of the cell was noted at 11 vdc. The Gamry Reference 3000 would not go below -11 vdc. Since no gassing occurred at -11 vdc, the reduction rate could most likely be much higher if voltage were increased. An even higher voltage and reduction rate are may be used they can be achieved with negligible oxygen production at the anode. The pH of the electrolyte at time zero is 4.46. The pH of the solution decreases to 4.29 after 35 minutes, and is 4.05 at the end of the experiment. The lowering of the pH indicates lithium ion removal from the electrolyte.

[0074] An amperage draw of -20 mA is noted at the start of the experiment. The amperage draw slowly increases to -60 mA after 30 minutes. The amperage holds fairly steady at this value for another 30 minutes. The experiment timer and graph are paused for 30 minutes to extend the experiment (voltage held at -11 vdc). After approximately 65 minutes of run time, a large amperage spike and sudden vigorous gassing is noted on the anode side of the cell. This is indicative of LiC-GC-BF 114/120 membrane failure.

[0075] Rapid gassing and bright white flame is observed when the cell 110 is opened and the cathode 124 side is exposed to electrolyte leaking through the LiC-GC-BF 114/120, evidencing that the cell produces lithium by electrolysis of lithium ions in a sulfuric acid aqueous solution, through a LiC- GC-BF 114/120 membrane system.

[0076] Turning now to Figures 4-6, a two-chamber deposition cell 200 that can be used to prepare pre-lithiated electrodes is shown. The two-chamber deposition cell 200 includes a first side 201 and a second side 202. In the following description and for ease of reference, the process of pre-lithiating an electrode using the two-chamber deposition cell 200 will be described with reference to pre-lithiating a cathode. To this end, the first side 201 will be referred to as an anode side 201 and the second side 202 will be referred to as the cathode side 202. However, one of skill will appreciate that, depending on the material forming the electrode to be pre-lithiated, either a cathode or an anode can be pre-lithiated.

[0077] With that in mind, the anode side 201 includes an anode, 215, an anolyte inlet 203 and an anolyte outlet 205 so that the anolyte flows past the anode 215 and can be recirculated using appropriate fluid connections and a pump (not shown). Accordingly, a lithium feed electrolyte solution is continuously fed or provided to the anolyte inlet 203 and circulated from the anolyte inlet 203 to the anolyte outlet 205 where the spent electrolyte is discharged via the anolyte outlet 205. Similarly, the cathode side 202 includes a catholyte inlet 204 and a catholyte outlet 206 so that the catholyte flows past the cathode 218 and can be recirculated using appropriate fluid connections and a pump (not shown). While any suitable type of pump can be used, a centrifugal pump has been found to be useful to minimize concentration gradients within the respective anolyte and catholyte.

[0078] A selective lithium ion conducting membrane 214, which may be supported and/or retained by retainer rings 215, is located between the anode side 201 and the cathode side 202 so that the anolyte is separate from the catholyte. The selective lithium ion conducting membrane 214 permits the selective flow of lithium from an aqueous lithium containing electrolyte (the anolyte) solution through the selective lithium ion conducting membrane 214 to the cathode side 202.

[0079] As shown in figures 4-6, the cathode 218 may be retained within the cathode side 202 by a retainer or holder 217 so that the cathode 218 is in contact with the catholyte, which may include a non-aqueous catholyte, examples of which are described herein.

[0080] A potential is applied while the anolyte and catholyte circulate through the anode side 201 and cathode side 202, respectively, to achieve lithium intercalation or plating on the cathode 218. The result is a pre-lithiated cathode. As noted earlier, while a method of pre-lithiating a cathode using the apparatus of figures 4-6 has been described, one of skill will understand that, depending on the material forming the electrode to be pre-lithiated, either a cathode or an anode can be pre-lithiated.

[0081] Use of the described apparatuses allows electrodes (anodes and cathodes) to be effectively pre-lithiated. To this end, the apparatuses and methods may be used to intercalate lithium (pre-lithiate the electrode) in an amount that was greater than the total theoretical graphite lithium intercalation capacity. In some instances, the described apparatuses and methods may be effective to prelithiate anodes to a level from about 100% to about 120% of the theoretical lithium intercalation capacity of the anode when conducted in combination with a non-lithium containing cathode.

[0082] Additionally or alternatively, for graphite based anodes, the apparatuses and methods may be used to intercalate lithium (pre-lithiate the electrode) from about 5% to about 30%, from about 10% to about 20%, or from about 15% to about 18% of the theoretical lithium intercalation capacity of the electrode (graphite based anode).

[0083] Additionally or alternatively, for hard carbons, Si or Sn containing active interaction materials, the described apparatuses and methods may be used to intercalate lithium (pre-lithiate the electrode) from about 10% to about 60%, from about 20% to about 40%, or from about 20% to about 30% of the theoretical lithium intercalation capacity of the electrode.

[0084] Additionally or alternatively, for cathodes, the apparatuses and methods may be used to intercalate lithium (pre-lithiate the electrode) from about 5% to about 30%, from about 10% to about 20%, or from about 10% to about 15% of the theoretical lithium intercalation capacity of the electrode (cathode).

[0085] Such pre-lithiated electrodes may be used in, for example lithium ion electrochemical cells or batteries the apparatuses and methods may be used to intercalate lithium (pre-lithiate the electrode) in an amount that ranges from amount from about 10 to about 20 percent of a theoretical lithium intercalation capacity of the electrode.

[0086] Conventional lithium ion batteries are typically electrode balanced relative to the amount of cathode material, e.g., lithium metal oxides or phosphates, which can be effectively coated onto a metal foil current collector such as aluminum foil. As a result, the lithium content is defined by the mass of cathode material. Upon charging, typically less than 20 microns of lithium transports to the anode structure. When the anode is formed of a carbon/graphite structure, the lithium is intercalated within the carbon/graphite structure as LiC6.

[0087] In next generation lithium cells, lithium may be plated onto lithium or the anode current collector. When plating lithium directly onto copper foil that is being used as the anode current collector, the plating may be more uniform if the current collector has been pre-nucleated with a layer of lithium or if it has been laminated to a thin foil of lithium metal. Neither of these methods is particularly desirable since a pre-layer of lithium from a vapor deposition process is slow and not cost effective, while the lithium foil approach requires lithium extrusion followed by roll thinning. Roll and bearing tolerances as well as the tendency for lithium to adhere to metal surfaces make this method a processing limited option. In addition, thinning lithium to less than 10 microns results in grain size issues as well as very low web tensile strength and tension control limitations. Variation in web tension can result in variation in material thickness or areal capacity variations. For cell safety and extended cycle life it is important that the capacity per area of a battery is extremely uniform.

[0088] In comparison, the described methods that include electrodeposition of lithium onto the anode current collector provides a method of pre-nucleation of the current collector enhancing in situ lithium plating uniformity during cell charging cycles. This approach may be beneficial when combined with a solid-state battery design utilizing a lithium anode. The process can be completed off-line or under optimized conditions in-line with cell manufacturing. When incorporated in-line, the plating area and current can be tailored for the resulting product requirements. The plating current can be linked to a web encoder adjusting the current per changes in the web speed.

[0089] It will be appreciated that the apparatuses shown in Figs. 1-6 and described above can be used in a method to produce a pre-lithiated electrode, such as a pre-lithiated cathode or a pre-lithiated anode. Such pre-lithiated electrodes are lithiated electrodes that have not undergone a charge cycle. The pre-lithiated electrodes are obtained using a selective lithium ion conducting layer to form highly pure lithium. The selective lithium ion conducting layer can comprise an active metal ion conducting glass or glass- ceramic. The selective lithium ion conducting layer, structure, or membrane may further comprise a lithium ion conductive barrier film.

[0090] The pre-lithiated electrode, whether it is a pre-lithiated cathode or pre-lithiated anode, is obtained by electrodepositing lithium onto an electrode using a selective lithium ion conducting layer. By using the selective ion conducting layer, the pre-lithiated electrode can be obtained by extracting lithium from a lithium salt. The lithium thus obtained can be free of metal impurities.

[0091] In one embodiment, the lithium can be free of at least one impurity selected from the group consisting of mercury, boron, sodium, aluminum, potassium, calcium, chromium, manganese, and nickel. The lithium obtained by the disclosed methods advantageously has a high purity, such as a purity of at least 99.96 weight percent on a metals basis, at least 99.99 weight percent on a metals basis, or at least 99.998 weight percent on a metal basis. [0092] Depending on the parameters used, such as the applied current, voltage, solution composition, and solution flow, the lithium obtained according to an embodiment of the present disclosure can assume a nano-rod morphology or a nano-sphere morphology such that upon cell charging a multitude of equivalent plating sites exist. In contrast, plating onto extruded- rolled lithium may limit the uniformity of preferred sites which can result in dendrite formation and eventually shorting between electrodes. Such dendrites limit cell life and the reduce product safety.

[0093] Any suitable cathode or anode can be pre-lithiated according to the process of this disclosure. Suitable anodes include, but are not limited to, a graphite anode, a hard carbon anode, a tin or silicon based anode, a mixture of graphite, hard carbon, tin, or silicon components, a lithium metal anode, a copper current collector, a graphite-based current collector and mixtures thereof. In conventional systems, the reactivity of lithium with the anode structure and electrolyte limits the materials which can be used as the anode. For example, soft graphite carbons possess a theoretical capacity of 372 mAh/g, while hard carbons have demonstrated a capacity of approximately 1000mAh/g. However, hard carbons have a very high level of irreversible capacity loss as high as 600 mAh/g during the first few charge cycles.

[0094] Suitable cathodes include, but are not limited to, may include electrochemically active materials such as: lithium cobalt dioxide, lithium nickel-manganese-cobalt (NMC) oxides in any ratio of these metals, lithium iron phosphate, lithium nickel oxide, lithium manganese spinel, lithium vanadium oxide, as well as other lithium based electrochemically active cathode materials and combinations thereof.

[0095] This same process of electrode lithiation can be applied to the cathode as a means of re-lithiation or cell lithium balancing. The balance of lithium content between the battery electrodes can be achieved by enhancing the lithium content of either the anode or cathode electrodes. In some situations, the cathode active material may not be stoichiometrically correct such as may be the case with recycled or reclaimed lithium metal oxide materials. The disclosed process of lithium intercalation-based electrodeposition, prior to cell assembly, can be utilized to increase the active lithium content and thus cell capacity.

[0096] The described pre-lithiated electrodes may advantageously be used in a battery. Suitable batteries include, but are not limited to, a lithium primary battery, a rechargeable lithium battery, a rechargeable lithium-ion battery, a thin film lithium-ion battery, a lithium-ion polymer battery, a lithium iron phosphate battery, a lithium sulfur battery, a solid-state lithium battery, a lithium air battery, and a nanowire battery. In some cases, the battery comprises recycled battery material. In some cases, recycling can be achieved by reclaiming and reconditioning cathode materials of lithium metal oxides.

[0097] Advantageously, the disclosed methods, compositions, and apparatuses may be used to provide more effective utilization of higher capacity carbon and other anodes, to provide a low cost means of utilizing lithium from recovered materials associated with hydrometallurgical lithium ion battery recycling, and to provide an effective method of replacing lithium content in cathode materials recovered from recycled lithium ion batteries. Further, the disclosed methods, compositions, and apparatuses can advantageously be used in conjunction with lithium metal-based anodes and solid-state lithium metal anodes.

[0098] Another application of the disclosed apparatuses and methods is to use a graphite substrate, either in the form of highly compressed graphite powder, such as that supplied by Neograf, or in the form of a three- dimensional porous carbon structure, such as carbon paper supplied by Toray. This substrate can serve multiple functions: electrical current collector, source for lithium ion intercalation, or substrate for plating nano-rods of lithium onto the surface of the graphite foil. The use of graphite foil for an anode collector, over copper foil, provides for a reduction in weight, cost, and compatibility with alternative cathodes such as those based on sulfur or organic polysulfides.

[0099] In accordance with the above description of the system and process, the following examples are presented to illustrate an exemplary application of the described system and process and are not meant to limit the claimed invention.

Example 1

[00100] A graphite-based anode electrode laminate on a copper current collector was obtained and is referred to as source 1 . The source 1 anode had a graphite loading of ~2.1 mAh/cm².

[00101] The graphite-based anode electrode laminate was pre-lithiated in the two-chamber deposition cell 200 shown in Figs 4-6, in which the aqueous solution side was separated from the organic electrolyte side by a ceramic lithium ion ceramic membrane 214 obtained from Ohara Corporation. The organic electrolyte chamber contained 1 M LiPF6 salt in a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) EC/DMC provided in a ratio of 1/1 v/v. The aqueous chamber consisted of lithium carbonate salt dissolved in sulfuric acid. The electrolyte was circulated within each chamber using a centrifugal pump to minimize any concentration gradients within the solutions.

[00102] The plating current was supplied using a Gamry Interface 1010E at a potential of -3.8 V for 120 minutes to intercalate lithium (pre-lithiate the electrode) in an amount that was greater than the total theoretical graphite lithium intercalation capacity of 372 mAh/g. After intercalating the lithium with the anode, the samples were rinsed in DMC.

[00103] Thereafter, circular electrode discs (approximately 15 mm diameter) were then punched from these samples and evaluated in 2032 type coin cells. The coin cells were assembled using a layered LiNio.5Mno.3Coo.2O2 (NMC532) cathode with an areal capacity (area-normalized specific capacity) of ~1.7 mAh/cm2 , pre-lithiated graphite anode (source 1) and liquid electrolyte comprising of 1 M LiPF6 in EC/EMC (1 :1 v/v ratio). One layer of Celgard 2325 separator was used between the electrodes to prevent them from coming in physical contact.

[00104] A reference coin cell was assembled using a non-pre-lithiated graphite anode from source 1 and tested for comparison. The reference cell and the cell according to the above description were galvanostatically cycled in the 3 - 4.1 V range using a constant current density of 0.17 mA/cm² (C/10- rate).

[00105] Figure 7 summarizes the cycling performance in terms of discharge capacity up to 100 cycles. The specific capacity values are expressed normalizing them to active cathode mass. It will be appreciated that the coin cell with pre-lithiated graphite anode delivered substantially higher capacity. Additionally, the first cycle Coulombic efficiency (CE) improved significantly upon pre-lithiation by 63% for non-pre-lithiated graphite vs. 86% for the pre- lithiated graphite. The improvement in first cycle CE and delivered capacity demonstrates the beneficial effect of anode pre-lithiation.

Example 2

[00106] A graphite-based anode electrode laminate on a copper current collector was obtained from two commercial sources, referred to as source A and source B. Active anode loadings were ~2.1 and 1 .75 mAh/cm² for source A and source B, respectively.

[00107] To confirm the viability and robustness of the described pre- lithiation process the following experiment was conducted. Two anodes from different suppliers, a current density ranging from 2 to 10 mA/cm², and a pre- lithiation level ranging from 10 to 20 percent of the theoretical graphite capacity. The anode electrode stock was pre-lithiated in the above-described two-chamber deposition cell 200 (shown in Figs. 4-6) in which the aqueous solution side was separated from the organic electrolyte side by a ceramic lithium ion ceramic membrane obtained from Ohara Corporation. The organic electrolyte chamber contained 1 M LiPF6 salt in an EC/DMC solution of a ratio of 1/1 v/v. The aqueous chamber contained lithium carbonate salt dissolved in sulfuric acid. The electrolyte was circulated within each chamber using a centrifugal pump to minimize any concentration gradients within the solutions. The current was supplied using a Gamry Interface 1010E to provide a current density ranging from 2 to 10 mA/cm² until achieving a pre-lithiation level of about 10 percent of the theoretical lithium intercalation capacity. After intercalating the lithium with the anode, the samples were rinsed in DMC.

[00108] Afterwards, circular anode discs (approximately 15 mm diameter) were punched out for coin cell assembly. 2032-type coin cells were assembled using a layered LiNio.8Mno.1Coo1O2 (NMC811) cathode with an areal capacity of ~1 .7 mAh/cm², pre-lithiated graphite anode and liquid electrolyte comprising of 1 M LiPF6 dissolved in EC/EMC (1 :1 v/v). One layer of Celgard 2325 separator was used between the electrodes to prevent them coming into physical contact.

[00109] Reference cells were assembled using non-pre-lithiated anode and tested for comparison. Both types of cells were galvanostatically cycled in the 3 - 4.2 V range using the following protocol. A constant rate of charge (C/10) for all cycles, but with varying rates of discharge: C/10 for first twenty cycles, followed by C/5 for next ten cycles, followed by C/2 for next ten cycles, which was then followed by C/10 rate discharge for additional ten cycles.

[00110] Figure 8 summarizes the cycling performance in terms of discharge capacity over 50 cycles for both graphite anodes (source A) that have been pre-lithiated to 10% of their specified capacities. The specific capacity values are expressed normalizing them to active cathode mass. The cells with pre- lithiated anodes delivered considerably higher capacities for both graphite anodes. Additionally, the first cycle Coulombic efficiency (CE) improved significantly upon pre-lithiation, 55% for non-pre-lithiated vs. 79% for the pre- lithiated anode from source A. [00111] Figure 9 summarizes the cycling performance in terms of discharge capacity over 50 cycles for both graphite anodes (source B) that have been pre-lithiated to 10% of their specified capacities. The specific capacity values are expressed normalizing them to active cathode mass. The cells with pre- lithiated anodes delivered considerably higher capacities for both graphite anodes. Additionally, the first cycle Coulombic efficiency (CE) improved significantly upon pre-lithiation, 60% for non-pre-lithiated vs. 71% for the pre- lithiated anode from source B.

[00112] The performance of the cells as compared on a cathode basis, y- axis of mAh/g of active NMC, LiNio.5Mno.3Coo.2O2 (NMC532), is significantly improved by the pre-lithiation process. Further, analysis of the pre-lithiation variables also confirmed that the desired conditions can be influenced by the anode composition, type of graphite, loading, and thickness. Of these variables, the anode graphite loading demonstrated a high correlation to the influences of the intercalation current density and optimal graphite loading. This is confirmed in Fig. 9.

[00113] Pre-lithiation factors such as percent lithiation and the rate of pre- lithiation can vary based on the type of graphite used as well as the graphite loading, which may be in the range of about 2 to about 5 mAh/cm². For anode A the best results were observed lower levels of pre-lithiation which were achievable at higher rates of intercalation. For anode B, the best results were observed at higher levels of pre-lithiation combined with a lower rate of intercalation. In this case, the cell performance results indicate that the pre- lithiation conditions need to be matched to the anode composition, loading, porosity, and lithium transport within the anode.

[00114] Figures 10 and 11 show the 50th discharge capacity for pre-lithiated anodes where the underlying electrodes were obtained from two different suppliers. In particular, figure 10 shows the predicted optimal deposition conditions for anode source B (noted above) and figure 11 shows the predicted optimal deposition conditions for anode source A (noted above).

The figures demonstrate the need to optimize lithium deposition including pre- lithiation conditions (percent deposition and current density) relative to the anode composition, materials, and active carbon loading. Example 3

[00115] A commercial silicon-graphite electrode was obtained and it comprised 20% silicon (30-50 nm) and 65% graphite (3-20 urn). The specified areal capacity of the anode was 2.4 mAh/cm². The electrode was pre-lithiated to 20% of the specified capacity at 2 mA/cm² in the above-described two- chamber deposition cell 200 (shown in Figs. 4-6).

[00116] The organic electrolyte used for pre-lithiation was 1 M LiPFe dissolved in EC/EMC (1 :1 v/v) and the aqueous chamber consisted of lithium carbonate salt dissolved in sulfuric acid. The anode laminate was dried under vacuum at 110°C overnight prior to pre-lithiation. The anode laminate was rinsed with DMC to wash away residual salt after pre-lithiation.

[00117] Afterwards, circular anode discs (approximately 15 mm diameter) were punched out for coin cell assembly. 2032-type coin cells were assembled using layered LiNio.5Mno.3Coo.2O2 (NMC532) cathode with an areal capacity of ~1 .9 mAh/cm², pre-lithiated Si-based anode and liquid electrolyte comprising of 1 M LiPFe dissolved in EC/EMC (1 :1 v/v). One layer of Celgard 2325 separator was used in between the electrodes to prevent them from coming into physical contact.

[00118] Reference cells were assembled using non-pre-lithiated anode.

Both the pre-lithiated and the non-pre-lithiated cells were galvanostatically cycled in the 3.1 - 4.1 V range using a constant current density of 0.1 mA/cm² (C/20-rate) for first three cycles followed by cycling at higher rate 0.49 mA/cm² (C/4-rate) in the subsequent cycles.

[00119] Figure 12 summarizes the cycling performance in terms of discharge capacity over 25 cycles. The specific capacity values are expressed normalizing them to active cathode mass. It is evident that the cell with pre- lithiated anode delivered higher capacity. Additionally, the first cycle Coulombic efficiency (CE) improved significantly upon pre-lithiation: 38% for non-pre-lithiated Si-based anode vs. 55% for the pre-lithiated Si-based anode. The first cycle CE and delivered capacity demonstrate the beneficial effect of anode pre-lithiation. [00120] It should be understood that various changes and modifications to the described embodiments will be apparent to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the present subject matter and without diminishing its intended advantages. It is therefore intended that such changes and modifications be covered by the appended claims.

[00121] Aspects of the invention are also set out in the following set of numbered clauses, in which is described:

[00122] 1. A pre-lithiated electrode that has not undergone a charge cycle, wherein lithium is electrodeposited onto an electrode using a selective ion conducting membrane.

[00123] 2. The pre-lithiated electrode of clause 1 , wherein the lithium is intercalated into or plated on the electrode.

[00124] 3. The pre-lithiated electrode of any of the preceding clauses, wherein the electrodeposited lithium is obtained by extracting lithium from a lithium salt using the selective ion conducting membrane.

[00125] 4. The pre-lithiated electrode of any of the preceding clauses, wherein the pre-lithiated electrode is a cathode or an anode.

[00126] 5. The pre-lithiated electrode of clause 5, wherein the pre-lithiated electrode is an anode and contains graphitic carbon, hard carbon, or lithium. [00127] 6. The pre-lithiated electrode of clause 5 wherein the intercalated or plated lithium is present in an amount from about 5% to about 30% of a theoretical lithium intercalation capacity of the anode.

[00128] 7. The pre-lithiated electrode of clause 5 wherein the pre-lithiated electrode is an anode and contains Si, Si alloys, Sn, Sn alloys, mixtures of carbon with Si, Si alloys, Sn, or Sn alloys.

[00129] 8. The pre-lithiated electrode of clause 7 wherein the intercalated or plated lithium is present in an amount from about 10% to about 60% of a theoretical lithium intercalation capacity of the anode.

[00130] 9. The pre-lithiated electrode of clause 5 wherein the pre-lithiated electrode is an anode combined with a copper current collector or a graphite- based current collector.

[00131] 10. The pre-lithiated electrode of clause 9 wherein the graphite based current collector is selected from the group consisting of carbon black, graphite, carbon nanotubes, carbon fibers, nitrogen doped carbon, and combinations thereof.

[00132] 11. The pre-lithiated electrode of clause 5, wherein the pre- lithiated electrode is a cathode.

[00133] 12. The pre-lithiated electrode of clause 11 wherein the intercalated or plated lithium is present in an amount from about 5% to about 30% of a theoretical lithium intercalation capacity of the cathode.

[00134] 13. The pre-lithiated electrode of clause 11 , wherein the cathode includes stoichiometric lithium metal oxides, non-stoichiometric lithium metal oxides or mixtures thereof.

[00135] 14. The pre-lithiated electrode of clause 13 wherein the stoichiometric lithium metal oxides, non-stoichiometric lithium metal oxides or mixtures thereof are obtained from hydrometallurgically processed recycled batteries.

[00136] 15. The pre-lithiated electrode of clause 11 , wherein the pre- lithiated electrode is a cathode that includes electrochemically active materials.

[00137] 16. The pre-lithiated electrode of clause 15 wherein the electrochemically active materials are selected from lithium cobalt dioxide, lithium nickel-manganese-cobalt (NMC) oxides, lithium iron phosphate, lithium nickel oxide, lithium manganese spinel, lithium vanadium oxide, lithium-based electrochemically active cathode materials, and combinations thereof.

[00138] 17. A battery including a cathode and an anode, wherein at least one of the cathode or the anode is pre-lithiated, has not undergone a charge cycle, and the lithium was electrodeposited onto an electrode using a selective ion conducting membrane.

[00139] 18. The battery of clause 17, wherein the battery comprises recycled battery material.

[00140] 19. A method of pre-lithiating an electrode, the method comprising electrodepositing lithium onto the electrode using a selective ion conducting membrane.

[00141] 20. The method of clause 19, wherein the lithium is provided by extracting the lithium from a lithium salt using the selective ion conducting membrane. [00142] 21 . The method clause 19 or 20 further comprising: providing an electrode in contact with an aqueous lithium-containing solution that is separated from an organic electrolyte by the selective ion conducting membrane; and applying a current potential at a level and for an amount of time sufficient to intercalate lithium within the anode.

[00143] 22. The method of clause 21 wherein the applied current is applied at a level and for an amount of time to intercalate in an amount that exceeds a total theoretical lithium intercalation capacity of the anode.

[00144] 23. The method of clause 21 wherein the applied current is applied at a level and for an amount of time to intercalate in an amount from about 5 to about 30 percent of a theoretical lithium intercalation capacity of the anode.

[00145] It will be understood that the invention has been described above purely by way of example, and modifications of detail can be made within the scope of the invention.

[00146] Each feature disclosed in the description, and (where appropriate) the claims and drawings may be provided independently or in any appropriate combination.

Claims

Claims:

1. A pre-lithiated electrode that has not undergone a charge cycle, wherein lithium is electrodeposited onto an electrode using a selective ion conducting membrane.

2. The pre-lithiated electrode of claim 1 , wherein the lithium is intercalated into or plated on the electrode.

3. The pre-lithiated electrode of any of the preceding claims, wherein the electrodeposited lithium is obtained by extracting lithium from a lithium salt using the selective ion conducting membrane.

4. The pre-lithiated electrode of any of the preceding claims, wherein the pre-lithiated electrode is a cathode or an anode.

5. The pre-lithiated electrode of claim 5, wherein the pre-lithiated electrode is an anode and contains graphitic carbon, hard carbon, or lithium.

6. The pre-lithiated electrode of claim 5 wherein the intercalated or plated lithium is present in an amount from about 5% to about 30% of a theoretical lithium intercalation capacity of the anode.

7. The pre-lithiated electrode of claim 5 wherein the pre-lithiated electrode is an anode and contains Si, Si alloys, Sn, Sn alloys, mixtures of carbon with Si, Si alloys, Sn, or Sn alloys.

8. The pre-lithiated electrode of claim 7 wherein the intercalated or plated lithium is present in an amount from about 10% to about 60% of a theoretical lithium intercalation capacity of the anode.

9. The pre-lithiated electrode of claim 5 wherein the pre-lithiated electrode is an anode combined with a copper current collector or a graphite-based current collector.

10. The pre-lithiated electrode of claim 9 wherein the graphite based current collector is selected from the group consisting of carbon black, graphite, carbon nanotubes, carbon fibers, nitrogen doped carbon, and combinations thereof.

11. The pre-lithiated electrode of claim 5, wherein the pre-lithiated electrode is a cathode.

12. The pre-lithiated electrode of claim 11 wherein the intercalated or plated lithium is present in an amount from about 5% to about 30% of a theoretical lithium intercalation capacity of the cathode.

13. The pre-lithiated electrode of claim 11 , wherein the cathode includes stoichiometric lithium metal oxides, non-stoichiometric lithium metal oxides or mixtures thereof.

14. The pre-lithiated electrode of claim 13 wherein the stoichiometric lithium metal oxides, non-stoichiometric lithium metal oxides or mixtures thereof are obtained from hydrometallurgically processed recycled batteries.

15. The pre-lithiated electrode of claim 11 , wherein the pre-lithiated electrode is a cathode that includes electrochemically active materials.

16. The pre-lithiated electrode of claim 15 wherein the electrochemically active materials are selected from lithium cobalt dioxide, lithium nickel- manganese-cobalt (NMC) oxides, lithium iron phosphate, lithium nickel oxide, lithium manganese spinel, lithium vanadium oxide, lithium-based electrochemically active cathode materials, and combinations thereof.

17. A battery including a cathode and an anode, wherein at least one of the cathode or the anode is pre-lithiated, has not undergone a charge cycle, and the lithium was electrodeposited onto an electrode using a selective ion conducting membrane.

18. The battery of claim 17, wherein the battery comprises recycled battery material.

19. A method of pre-lithiating an electrode, the method comprising electrodepositing lithium onto the electrode using a selective ion conducting membrane.

20. The method of claim 19, wherein the lithium is provided by extracting the lithium from a lithium salt using the selective ion conducting membrane.

21 . The method claim 19 or 20 further comprising: providing an electrode in contact with an aqueous lithium-containing solution that is separated from an organic electrolyte by the selective ion conducting membrane; and applying a current potential at a level and for an amount of time sufficient to intercalate lithium within the anode.

22. The method of claim 21 wherein the applied current is applied at a level and for an amount of time to intercalate in an amount that exceeds a total theoretical lithium intercalation capacity of the anode.

23. The method of claim 21 wherein the applied current is applied at a level and for an amount of time to intercalate in an amount from about 5 to about 30 percent of a theoretical lithium intercalation capacity of the anode.