Anode materials for rechargeable lithium-ion batteries and methods for making and using same

Abstract

A lithium-ion battery anode material is disclosed that includes a surface-coated disordered rock-salt lithium vanadium oxide. The surface coating includes a species selected from the group consisting of carbon, metal oxide, metalloid oxide, metal fluoride, metalloid fluoride, metal phosphate, metalloid phosphate, and combinations thereof. Materials, design, synthesis methods, and devices related to fast-charging lithium-ion batteries are provided. The present invention fills a technology gap by providing an anode material having a disordered rock-salt lithium vanadium oxide that achieves fast charging in 10 minutes or less, energy density in excess of 200 W·h / kg, a life of at least 10,000 cycles, and improved battery safety. Methods of making and using the optionally surface-coated disordered rock-salt lithium vanadium oxide are disclosed. Numerous experimental examples are included that demonstrate several noteworthy attributes of this battery technology.

Description

[Technical field]

[0001] Technical Field This international patent application claims priority to U.S. Provisional Patent Application No. 63 / 255,953, filed October 14, 2021, U.S. Provisional Patent Application No. 63 / 295,455, filed December 30, 2021, and U.S. Provisional Patent Application No. 17 / 877,239, filed July 29, 2022, each of which is incorporated herein by reference.

[0002] The present disclosure relates generally to lithium-ion batteries. More specifically, various embodiments relate to improved anode materials for lithium-ion batteries. [Background technology]

[0003] background Rechargeable lithium-ion (Li-ion) batteries that can be safely charged and discharged at high speeds are desirable for electrified transportation, portable electronics, grid storage, and other applications. Rechargeable Li-ion batteries have become an essential necessity for mobile devices and personal computers in modern society. Although significant advances in battery technology (e.g., energy density and structural stability) continue to be made, fast charging is still an area in need of significant advances for Li-ion batteries. Li-ion batteries can possess high energy density, but the rate at which the battery can be charged is limited by the battery's anode material.

[0004] Graphite has been the primary anode material for rechargeable lithium-ion batteries due to its low cost, high reversibility, and working potential close to that of lithium metal. These attributes enable batteries with high specific energy and long cycle life. Current commercially available high-energy density Li-ion batteries based on graphite anodes have achieved high energy densities of over 250 W·h / kg. However, these Li-ion batteries require several hours to charge. The demand for ultra-fast charging poses a major challenge for graphite. At high charging rates, the graphite anode potential can fall below that of the lithium coating, leading to lithium deposition and associated loss of life and safety. Reducing the battery charging time to minutes sacrifices energy and significantly reduces cycle life in Li-ion batteries using graphite anodes.

[0005] The lithium coating can be overcome by slightly increasing the anode potential. The state-of-the-art commercially available anode for ultra-fast charging Li-ion batteries is lithium titanate, Li4Ti5O 12 (LTO). 12 Li4Ti5O is a generally safe material and can be charged in less than 10 minutes for many cycles, but its energy density is less than 90Wh·h / kg. 12 The potential of Li / Li + This gives a total voltage of about 1.5 V for a Li-ion battery, which, when combined with a commercially available 4 V cathode, results in a 2.5 V Li-ion battery. Due to its low energy density, LTO applications are primarily limited to buses and utility vehicles.

[0006] LiV 0.5 Ti 0.5The potential of other intercalation anodes such as S2 is about 1 V, which is still much higher than desired. Alloy anodes (e.g., anodes using aluminum alloys) may have an ideal potential of 0.5 V and high capacity, but their cycling stability is questionable even under normal operating conditions, let alone ultra-fast charging. None of the state-of-the-art systems can achieve both high power density combined with high energy density, thus creating a technology gap. Summary of the Invention [Problem to be solved by the invention]

[0007] overview There remains a need for improved anode materials for Li-ion batteries, particularly Li-ion battery anodes that can be fast charged in less than 10 minutes, have an energy density of at least 200 Wh·h / kg, and are capable of operating for at least 20,000 cycles without compromising the safety of the battery. [Means for solving the problem]

[0008] SUMMARY OF THE DISCLOSURE The present disclosure addresses the aforementioned needs in the art, as summarized and then described in further detail below.

[0009] Some variations provide an anode material comprising a plurality of anode material particles, where the anode material particles comprise an internal phase comprising lithium vanadium oxide and a surface coating disposed on an outer surface of the internal phase, the lithium vanadium oxide being Li a V b O c (a=0.001 to 10, b=1 to 3, c=1 to 9, and a, b, and c are Li a V b O c (selected to balance the charge of Li a V b O cis capable of being reversibly lithiated, and the surface coating comprises a species selected from the group consisting of carbon, a metal oxide, a metalloid oxide, a metal fluoride, a metalloid fluoride, a metal phosphate, a metalloid phosphate, and combinations thereof.

[0010] In some embodiments, the surface coating comprises carbon. The carbon may be predominantly sp type, predominantly sp 2 Type, or mainly sp 3 In some embodiments, the carbons may be of the sp carbon and sp carbon. 2 Carbon combinations, sp carbon and sp 3 Carbon combination, sp 2 Carbon and sp 3 Combinations of carbons, or sp carbons, sp 2 Carbon and sp 3 It is a combination of carbon.

[0011] When the surface coating includes carbon, the carbon can be in the form of graphene, graphite, carbon nanotubes, carbon fibers, ultrafine carbon, carbon black, nanodiamonds, hard carbon, soft carbon, or combinations thereof.

[0012] In some embodiments, the surface coating has an average coating thickness selected from about 0.1 nanometers to about 100 nanometers.

[0013] In some embodiments, the anode material particles have a shape selected from the group consisting of spherical, cylindrical, cubic, irregular, and combinations thereof. The anode material particles can have, for example, an average effective diameter selected from about 0.01 microns to about 100 microns.

[0014] In some embodiments, the surface coating is a non-porous coating that does not have gaps. In other embodiments, the surface coating is a porous coating. The surface coating can have an average porosity selected from, for example, about 1% to about 95%.

[0015] In some embodiments, the anode material is characterized as being chemically stable in the presence of air. In these or other embodiments, the anode material is characterized as being chemically stable in the presence of water.

[0016] In some embodiments, Li a V b O c is crystalline. Preferably, Li a V b O c At least 10% by weight of

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[0017] Li a V b O cLi3V2O5, Li4V2O5, Li5V2O5, LiV2O5, Li 0.001 V2O5, Li2V2O5, Li 0.001 VO2, LiVO2, Li2VO2, Li 0.001 VO3, LiVO3, Li2VO3, Li3VO3, Li 0.001 V3O8, LiV3O8, Li2V3O8, Li3V3O8, Li 0.001 V2O3, LiV2O3, Li2V2O3, Li3V2O3, and combinations thereof.

[0018] In some embodiments, the lithium vanadium oxide is a compound having a composition of Li a V b O c M d (d=0.001 to 3, and a, b, c, and d are Li a V b O c M d The lithium vanadium oxide further comprises a dopant M that is chemically or physically contained within the lithium vanadium oxide provided by a V b O c M d can be reversibly lithiated. The dopant M can be selected from the group consisting of Be, Mg, Ca, Zn, Fe, Cu, Sc, B, Y, Al, La, Si, Ge, Sn, Ti, Zr, Mn, P, Nb, Ta, Cr, Mo, W, Se, and combinations thereof. Preferably, when the lithium vanadium oxide further comprises a dopant M, Li a V b O c Approximately 10% to 100% by weight of

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[0019] In some embodiments, the anode material further comprises one or more additional anode material components selected from the group consisting of silicon, silicon oxide, tin, tin oxide, phosphorus, carbonaceous species, and combinations thereof, where the carbonaceous species is different from the carbon (if any) contained in the surface coating. The carbonaceous species can be graphite, non-graphitized carbon, or combinations thereof.

[0020] The anode material may, for example, be about 1.5 g / cm 3 ~Approx. 4.5g / cm 3 The anode material may have a volume porosity of, for example, selected from about 5% to about 80%.

[0021] In a preferred embodiment, Li a V b O c is the amount of Li a V b O c undergoes a volume change of about 0% to about 20%. Preferably, Li a V b O c The volume change is about 0% to about 10%, and more preferably about 0% to about 5%.

[0022] Some variations of the present invention provide anodes that include the disclosed anode materials.

[0023] The anode may further include one or more additional anode components selected from the group consisting of silicon, silicon oxide, tin, tin oxide, phosphorus, carbonaceous species, and combinations thereof, where the carbonaceous species is different from the carbon (if any) contained in the surface coating. The additional anode components may collectively range in a total concentration of, for example, about 0.25% to about 80% by weight of the anode.

[0024] When the anode includes a carbonaceous species, the carbonaceous species can be graphite, non-graphitized carbon, or a combination thereof.

[0025] In some embodiments, the anode further comprises one or more binders. The binder can be, for example, an aqueous binder selected from the group consisting of carboxymethyl cellulose, styrene-butadiene rubber, styrene-butadiene copolymer, polyacrylic acid, lithium substituted polyacrylic acid, and combinations thereof. Alternatively or additionally, the binder can be, for example, a non-aqueous binder selected from the group consisting of polyvinylidene fluoride, poly(vinylidene fluoride-co-hexafluoropropylene), and combinations thereof. The concentration of the binder can be, for example, in the range of about 0.25% to about 50% by weight of the anode.

[0026] In some embodiments, the anode has an anode volume porosity selected from about 5% to about 80%.

[0027] In some embodiments, the anode has an average anode thickness of about 200 nanometers to about 500 microns.

[0028] The anode can be present in the cell. In a typical cell, there are multiple anode layers, multiple cathode layers, multiple separator layers, each disposed between an individual anode layer and cathode layer, and a packet foil surrounding the multi-layered substructure (i.e., multiple anode layers, multiple separator layers, and multiple cathode layers). Each separator layer is configured to electrically isolate the anode layer from the cathode layer. The anode can be disposed on a first substrate (e.g., copper foil) and the cathode can be disposed on a second substrate (e.g., aluminum foil). In a layered cell configuration, there are typically many layers of anodes, first substrates, separators, cathodes, and second substrates.

[0029] In some embodiments, the anode has a loading of anode material selected from about 20% to about 100% by weight. In some embodiments, the anode has a loading of about 0.2 mg / cm on at least one side of the anode. 2 ~50mg / cm 2 In some embodiments, the anode has an areal loading of about 0.05 mA·h / cm on at least one side of the anode. 2 ~Approx. 10mA h / cm 2 The anode material has an areal capacity selected from:

[0030] The cathode is LiFePO4, LiMn2O4, LiNi 0.5 Mn 1.5 O4, LiNi x Co y Mn z O2(x+y+z=1), LiCoO2, LiNi x Co y Al z O2(x+y+z=1), LiFe x Mn y PO4(x+y=1), aLiNi x Co y Mn zThe cathode material may comprise a material selected from the group consisting of O2·(1-a)Li2MnO3 (where a=0 to 1 and x+y+z=1), and combinations thereof.

[0031] In some embodiments, the cell further comprises an electrolyte, which may be selected from a liquid electrolyte, a polymer gel electrolyte, a solid electrolyte, or a combination thereof.

[0032] Another variation of the present invention provides a method for synthesizing an anode material, the method comprising the steps of: (a) applying a reducing agent to a precursor material, the reducing agent comprising lithium, the precursor material comprising vanadium oxide, vanadium lithium oxide, or a combination thereof, thereby producing a reduced material; (b) introducing a surface coating onto the reduced material after and / or during step (a), the surface coating comprising a species selected from the group consisting of carbon, metal oxides, metalloid oxides, metal fluorides, metalloid fluorides, metal phosphates, metalloid phosphates, and combinations thereof; (c) recovering an anode material comprising a plurality of anode material particles, the anode material particles comprising an internal phase comprising lithium vanadium oxide and a surface coating disposed on an outer surface of the internal phase, the lithium vanadium oxide being Li a V b O c (a=0.001 to 10, b=1 to 3, c=1 to 9, and a, b, and c are Li a V b O c (selected to balance the charge of Li a V b O c includes being capable of being reversibly lithiated.

[0033] In some ways, Li a V b O c At least 10% by weight of

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[0034] In some methods, the precursor material includes V2O5, LiV2O5, Li2V2O5, or a combination thereof.

[0035] In some methods, the reducing agent is butyllithium (LiC4H9), lithium naphthalene (LiC 10 H8), Lithium Anthracenide (LiC 14 H9), and combinations thereof. In certain embodiments, the reducing agent is lithium naphthalene prepared by dissolving lithium in a solution comprising naphthalene and a solvent, where the solvent is selected from the group consisting of tetrahydrofuran, 1,2-dimethoxyethane, dimethyl carbonate, and combinations thereof.

[0036] In some methods, the precursor material further comprises a dopant M. The dopant M may be selected from the group consisting of Be, Mg, Ca, Zn, Fe, Cu, Sc, B, Y, Al, La, Si, Ge, Sn, Ti, Zr, Mn, P, Nb, Ta, Cr, Mo, W, Se, and combinations thereof.

[0037] In some ways, Li a V b O c is the amount of Li a V b O cundergoes a volume change of about 0% to about 20%, for example, about 0% to about 10%, or about 0% to about 5%.

[0038] Some methods are Dissolving the precursor material (e.g., using H2O2) to form a sol-gel; mixing a precursor of the surface coating with the sol-gel to form a homogenous mixture; drying the homogenous mixture, thereby forming a dry powder; calcining the dried powder in air, whereby the precursor of the surface coating is converted to the surface coating; recovering the anode material particles; and Further includes:

[0039] When the surface coating of step (b) contains carbon, the carbon may be of the sp type, sp 2 Type and / or sp 3 The carbon can be in the form of graphene, graphite, carbon nanotubes, carbon fibers, ultrafine carbon, carbon black, nanodiamond, hard carbon, soft carbon, or combinations thereof.

[0040] In some methods, the precursor material has a precursor material shape selected from the group consisting of spherical, cylindrical, cubic, irregular, and combinations thereof.

[0041] In some methods, the precursor material has an average effective diameter selected from about 0.1 microns to about 100 microns. The precursor material may have a bimodal particle size distribution.

[0042] In some methods, the precursor material is V2O5. V2O5 can be present in the precursor material in a purity range of, for example, about 90% to about 100% by weight.

[0043] The surface coating can have an average coating thickness selected from, for example, about 0.1 nanometers to about 100 nanometers. The surface coating can have an average porosity selected from, for example, about 0% to about 95%.

[0044] The anode material can have a volume porosity of the anode material selected, for example, from about 5% to about 80%.

[0045] The method may further include introducing one or more additional components to the anode material, optionally selected from the group consisting of silicon, silicon oxide, tin, tin oxide, phosphorus, carbonaceous species, and combinations thereof, where the carbonaceous species is different from the carbon (if any) contained in the surface coating.

[0046] The method may further include introducing into the anode one or more binders selected from the group consisting of carboxymethyl cellulose, styrene-butadiene rubber, styrene-butadiene copolymer, polyacrylic acid, lithium substituted polyacrylic acid, polyvinylidene fluoride, and combinations thereof.

[0047] In some methods, the cathode material is cast in multiple layers on the second substrate to form multiple cathode layers. A separator layer is disposed on each of the multiple anode layers, and each of the cathode layers is laminated on the separator layer. A packet foil is configured to surround the multiple anode layers, the multiple separator layers, and the multiple cathode layers to form a cell.

[0048] In some methods, the lithiated anode has a loading of anode material selected from about 20% to about 100% by weight. In some methods, the lithiated anode has a loading of about 0.2 mg / cm on at least one side of the lithiated anode. 2 ~about 50mg / cm 2 In some methods, the lithiated anode has a surface loading of the anode material selected from about 0.05 mA·h / cm on at least one side of the lithiated anode.2 ~Approx. 10mA h / cm 2 The anode material has an areal capacity selected from:

[0049] The method further comprises, following step (c), cycling Li a V b O c In the lithiation-delithiation cycle, Li a V b O c preferably undergoes a volume change of about 0% to about 20%, more preferably about 0% to about 10%, and most preferably about 0% to about 5% during lithiation-delithiation cycling.

[0050] Yet another variation of the present invention provides a method of manufacturing a cell, the method comprising the steps of: (a) casting an anode material onto a first substrate to form an anode, the anode material comprising a plurality of anode material particles, the anode material particles comprising an internal phase comprising lithium vanadium oxide and an optional surface coating disposed on an external surface of the internal phase, the lithium vanadium oxide being Li x V y O z (x=0 to 10, y=1 to 3, z=1 to 9, and x, y, and z are Li x V y O z (selected to maintain a charge balance of (b) applying a reducing agent to the anode material, the reducing agent comprising lithium, whereby Li a V b O c (a=0.001 to 10, b=1 to 3, c=1 to 9, and a, b, and c are Li a V b O c (selected to maintain charge balance of Li a V b O c can be reversibly lithiated; (c) optionally removing excess reducing agent (if any) from the lithiated anode material; and (d) casting a cathode material onto a second substrate to form a cathode; (e) laminating a separator to the anode; (f) laminating a cathode to the separator; (g) surrounding the plurality of anode layers, the plurality of separator layers, and the plurality of cathode layers with a packet foil to form a cell; Includes.

[0051] Some methods of manufacturing cells use Li x V y O z is V2O5, Li 0.001 V2O5, LiV2O5, Li2V2O5, Li3V2O5, Li4V2O5, Li5V2O5, and combinations thereof.

[0052] Some methods of manufacturing cells use Li a V b O c At least 10% by weight of

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[0053] In some methods of manufacturing the cell, a surface coating is present and disposed on the outer surface of the internal phase, where the surface coating comprises a species selected from the group consisting of carbon, metal oxides, metalloid oxides, metal fluorides, metalloid fluorides, metal phosphates, metalloid phosphates, and combinations thereof.

[0054] If a surface coating is present and contains carbon, the carbon may be sp 2 Type and / or sp 3 Exemplary forms of carbon include graphene, graphite, carbon nanotubes, carbon fibers, ultrafine carbon, carbon black, nanodiamond, hard carbon, soft carbon, or combinations thereof.

[0055] In some methods of manufacturing the cell, the anode material further comprises a dopant M, where the dopant M is optionally selected from the group consisting of Be, Mg, Ca, Zn, Fe, Cu, Sc, B, Y, Al, La, Si, Ge, Sn, Ti, Zr, Mn, P, Nb, Ta, Cr, Mo, W, Se, and combinations thereof.

[0056] The method of manufacturing the cell may further include introducing one or more additional components selected from the group consisting of silicon, silicon oxide, tin, tin oxide, phosphorus, carbonaceous species, and combinations thereof into the anode material, where the carbonaceous species, when present, is different from the carbon (if any) contained in the surface coating.

[0057] The method of manufacturing the cell may further include introducing one or more binders selected from the group consisting of carboxymethyl cellulose, styrene-butadiene rubber, styrene-butadiene copolymer, polyacrylic acid, lithium substituted polyacrylic acid, polyvinylidene fluoride, and combinations thereof into the anode material.

[0058] Some methods of manufacturing cells use Li a V b O cis the amount of Li a V b O c However, the volume of the liquid crystal display device is changed by about 0% to about 20%, preferably by about 0% to about 10%, and more preferably by about 0% to about 5%.

[0059] In some methods of manufacturing the cell, the anode has a loading of anode material selected from about 20% to about 100% by weight.

[0060] In some methods of manufacturing the cell, the anode comprises about 0.2 mg / cm2 of carbon nanotube on at least one side of the anode. 2 ~about 50mg / cm 2 The surface load of the anode material is selected from:

[0061] In some methods of manufacturing the cell, the anode has a current density of about 0.05 mA·h / cm on at least one side of the anode. 2 ~Approx. 10mA h / cm 2 The anode material has an areal capacity selected from:

[0062] The method of manufacturing the cell may further include injecting an electrolyte into the cell.

[0063] In some methods of manufacturing the cell, the first substrate can be, for example, a copper foil having a thickness of about 1 micron to about 100 microns, and the second substrate can be, for example, an aluminum foil having a thickness of about 1 micron to about 100 microns.

[0064] Yet another variation of the present invention provides a method of manufacturing a cell, the method comprising the steps of: (a) casting an anode material onto a first substrate to form an anode, the anode material comprising a plurality of anode material particles, the anode material particles comprising Li x V y O z (x=0 to 10, y=1 to 3, z=1 to 9, and x, y, and z are Li x V y O zan optional surface coating disposed on an outer surface of the internal phase; (b) pressing lithium into the anode to form a pressed anode; (c) casting a cathode material onto a second substrate to form a cathode; (d) laminating a separator onto the pressed anode; (e) laminating a cathode to a separator; (f) surrounding the plurality of anode layers, the plurality of separator layers, and the plurality of cathode layers with a packet foil to form a cell; (g) injecting an electrolyte into the cell; and (h) Press the anode with Li a V b O c (a=0.001 to 10, b=1 to 3, c=1 to 9, and a, b, and c are the same as those described above.) a V b O c (selected to maintain charge balance of Li a V b O c can be reversibly lithiated; Includes.

[0065] Some methods of manufacturing cells use Li x V y O z is V2O5, Li 0.001 Li is selected from the group consisting of V2O5, LiV2O5, Li2V2O5, Li3V2O5, Li4V2O5, Li5V2O5, and combinations thereof. x V y O z can be present in the internal phase in an internal phase purity range of, for example, about 90% by weight to about 100% by weight.

[0066] In some methods of manufacturing the cell, the anode material particles have a shape of the anode material selected from the group consisting of spherical, cylindrical, cubic, irregular, and combinations thereof.

[0067] In some methods of manufacturing a cell, the Li formed in step (g) a V b O c At least 10% by weight of

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[0068] In some methods of manufacturing the cell, a surface coating is present and disposed on the outer surface of the internal phase. The surface coating can include a species selected from the group consisting of carbon, metal oxides, metalloid oxides, metal fluorides, metalloid fluorides, metal phosphates, metalloid phosphates, and combinations thereof.

[0069] If a surface coating is present and contains carbon, the carbon may be sp 2 Type and / or sp 3 Exemplary forms of carbon include graphene, graphite, carbon nanotubes, carbon fibers, ultrafine carbon, carbon black, nanodiamond, hard carbon, soft carbon, or combinations thereof.

[0070] In some methods of manufacturing the cell, the anode material further comprises a dopant M, where dopant M is selected from Be, Mg, Ca, Zn, Fe, Cu, Sc, B, Y, Al, La, Si, Ge, Sn, Ti, Zr, Mn, P, Nb, Ta, Cr, Mo, W, Se, and any combination thereof.

[0071] Some methods of manufacturing the cell further include introducing one or more additional components to the anode material selected from the group consisting of silicon, silicon oxide, tin, tin oxide, phosphorus, carbonaceous species, and combinations thereof, where the carbonaceous species, when present, is different from the carbon (if any) contained in the surface coating.

[0072] Some methods of manufacturing the cell further include incorporating into the anode one or more binders selected from the group consisting of carboxymethyl cellulose, styrene-butadiene rubber, styrene-butadiene copolymer, polyacrylic acid, lithium substituted polyacrylic acid, polyvinylidene fluoride, and combinations thereof.

[0073] Some methods of manufacturing cells use Li a V b O c is the amount of Li a V b O c However, the volume of the liquid crystal display device is changed by about 0% to about 20%, preferably by about 0% to about 10%, and more preferably by about 0% to about 5%.

[0074] In some methods of manufacturing the cell, the anode comprises a loading of about 0.2 mg / cm of an anode material selected from about 20% by weight to about 100% by weight on at least one side of the anode. 2 ~about 50mg / cm 2 and a surface loading of the anode material selected from the group consisting of about 0.05 mA·h / cm on at least one side of the anode. 2 ~Approx. 10mA h / cm 2 The anode material has an areal capacity selected from:

[0075] In some methods of manufacturing the cell, the first substrate can be, for example, a copper foil having a thickness of about 1 micron to about 100 microns, and the second substrate can be, for example, an aluminum foil having a thickness of about 1 micron to about 100 microns.

[0076] In some methods of manufacturing the cell, step (b) does not utilize a solvent to form the pressed anode.

[0077] In some methods of manufacturing the cell, steps (f) and (g) are performed simultaneously rather than sequentially. [Brief description of the drawings]

[0078] BRIEF DESCRIPTION OF THE DRAWINGS [Figure 1] FIG. 1 is a schematic diagram of carbon-coated V2O5 and carbon-coated disordered rock salt lithium vanadium oxide (DRS-LVO) in some embodiments of the present invention. [Diagram 2] FIG. 1 is a schematic diagram of the chemical synthesis of disordered rocksalt lithium vanadium oxide from starting V2O5 powder according to some embodiments of the present invention. [Diagram 3] FIG. 2 is a schematic diagram of an in situ electrochemical reaction for the synthesis of disordered rocksalt lithium vanadium oxide from V2O5 according to some embodiments of the present invention. [Figure 4] FIG. 1 shows images taken using scanning electron microscopy (SEM) of uncoated and carbon-coated V2O5 according to examples herein, illustrating that for the carbon-coated V2O5, carbon particles cover the surface of the V2O5 particles. [Diagram 5] 1 shows SEM images of disordered rock-salt Li3V2O5 powders with various morphologies, according to examples herein. [Figure 6]FIG. 1 shows X-ray diffraction (XRD) graphs of disordered rocksalt lithium vanadium oxide prepared by various methods according to the examples herein, and the stability of the disordered rocksalt lithium vanadium oxide after one month in air, demonstrating that stable pure-phase disordered rocksalt Li3V2O5 can be synthesized from V2O5 powder by chemical methods. [Figure 7] 1 shows an XRD graph of a disordered rock-salt Li3V2O5 anode material prepared by in situ electrochemical reaction according to an embodiment of the present specification, illustrating that phase-pure disordered rock-salt Li3V2O5 can be synthesized from V2O5 by in situ electrochemical reaction. [Figure 8] FIG. 13 shows the charge / discharge voltage profile of a Li3V2O5 electrode prepared by in situ electrochemical reaction according to an embodiment of the present specification. [Figure 9] 2 shows XRD graphs of V2O5 and carbon-coated V2O5 according to an embodiment of the present specification, showing that the carbon-coated V2O5 maintains the original structure of V2O5. [Figure 10] 1 shows XRD graphs of V2O5 and CNT (carbon nanotube) coated V2O5 according to an embodiment of the present specification, showing that the CNT coated V2O5 maintains the original structure of V2O5. [Figure 11] 13 shows the capacity retention of Li3V2O5 and CNT-coated Li3V2O5 at various charge / discharge current rates according to the examples herein, indicating that CNT-coated Li3V2O5 has better fast charging capability. [Figure 12] 1 shows a graph illustrating the cycling stability of a disordered rocksalt Li3V2O5 anode after more than 50 cycles at a temperature of -20°C, according to an embodiment of the present specification. [Figure 13] 1 shows a graph showing the cycling stability of a Li3V2O5 electrode after more than 25 cycles at a temperature of 60° C. according to an embodiment of the present specification. [Figure 14]13 shows a graph showing charge / discharge voltage profiles of a disordered rock-salt Li3V2O5||LiNi0.8Mn0.1Co0.1O2 full cell at various charge / discharge rates, illustrating fast charging capability, according to an embodiment herein. [Figure 15] 13 shows a graph showing the cycling performance of a disordered rock-salt Li3V2O5||LiNi0.8Mn0.1Co0.1O2 full cell when cycled at a 5 min charge / discharge rate, demonstrating long-term stability, according to examples herein. [Figure 16] 1 shows XRD graphs of disordered rock salt Li3V2O5 prepared from V2O5 of various purities according to examples herein. [Figure 17] 1 shows XRD graphs of disordered rock salt Li3V2O5 and disordered rock salt Li4V2O5 synthesized via wet chemical reaction according to an embodiment of the present specification. [Figure 18] 1 shows an XRD graph demonstrating the water stability of disordered rock salt Li3V2O5, according to an embodiment of the present specification. [Figure 19] 13 shows the voltage profile of disordered rock salt Li3V2O5 at C / 2 rate, according to an embodiment of the present specification. [Figure 20] 13 shows the capacity retention of disordered rock salt Li3V2O5 at various charge / discharge current rates, according to an embodiment of the present specification. [Figure 21] 1 shows XRD graphs of disordered rock salt Li3V2O5 in the charged and discharged states according to an embodiment of the present specification. [Figure 22] 13 shows the capacity retention of disordered rock salt Li3V2O5 with CMC binder at various charge / discharge current rates, according to an embodiment herein. [Figure 23] 13 shows voltage profiles of disordered rock salt Li3V2O5 at various charge / discharge current rates, according to examples herein. [Figure 24] 1 illustrates the performance of disordered rock salt Li3V2O5 in carbonate electrolyte and the capacity retention of the disordered rock salt Li3V2O5 at various charge / discharge current rates, according to an embodiment of the present specification. [Diagram 25]13 shows voltage profiles of disordered rock salt Li3V2O5 at various charge / discharge current rates, according to examples herein. [Figure 26] 1 illustrates the performance of disordered rock-salt Li3V2O5 in an ester-based electrolyte and the capacity retention of the disordered rock-salt Li3V2O5 at various charge / discharge current rates, according to an embodiment of the present specification. [Figure 27] 13 shows voltage profiles of disordered rock salt Li3V2O5 at various charge / discharge current rates, according to examples herein. [Figure 28] 13 shows the long-term cycling performance of disordered rock salt Li3V2O5 at a rate of C / 2, according to an embodiment of the present specification. [Figure 29] FIG. 13 shows the performance of disordered rock-salt Li3V2O5 in an ether-based electrolyte with high localized concentration according to an embodiment herein, and shows the voltage profile of the disordered rock-salt Li3V2O5 at various charge / discharge current rates. [Diagram 30] 13 shows the long-term cycling performance of disordered rock salt Li3V2O5 at a rate of 20C according to an embodiment of the present specification. [Diagram 31] 13 shows SEM and EDX analysis of a Li metal counter electrode from Li|| disordered rock salt Li3V2O5 cycled at 60° C. according to an embodiment of the present specification. [Diagram 32] 13 shows EDX elemental analysis of C, O, F, and P of a Li metal counter electrode from Li|| disordered rock salt Li3V2O5 cycled at 60 °C according to an embodiment of the present specification. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0079] Detailed Description of the Invention The principles, compositions, materials, systems, and methods of the present disclosure will now be described in detail with reference to various non-limiting embodiments of the technology.

[0080] This description enables a person skilled in the art to practice and use the technology and describes several embodiments, adaptations, variations, alternatives, and uses of the technology. These and other embodiments, features, and advantages of the technology will become more apparent to those skilled in the art upon review of the following detailed description in conjunction with the accompanying drawings.

[0081] 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 technology belongs.

[0082] Unless otherwise indicated, all numerical values ​​expressing conditions, concentrations, dimensions, and the like used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless otherwise indicated, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending at least on particular analytical techniques.

[0083] The term "comprising" is synonymous with "including," "containing," or "characterized by" and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. "Comprising" is a term used in claim language to mean that a specified claim element is essential, but that other claim elements can be added and still form a structure within the scope of the claim.

[0084] As used herein, the phrase "consisting of" excludes any element, step, or ingredient not specified in the claim. When the phrase "consisting of" (or variations thereof) appears in a clause in the body of a claim rather than immediately following the preamble, it limits only the elements recited in that clause and does not exclude other elements from the claim as a whole. As used herein, the phrase "consisting essentially of" limits the scope of a claim to certain elements or method steps, as well as to those that do not materially affect the basic and novel features of the claimed subject matter.

[0085] With respect to the terms "comprising" (and equivalently "including"), "consisting of" and "consisting essentially of," when one of these three terms is used herein, the disclosed and claimed subject matter may include the use of either of the other two terms, except as used by the Markush Group. Thus, in some embodiments not expressly stated otherwise, any instance of "comprising" may be replaced with "consisting of" or alternatively "consisting essentially of." The term "including" should be interpreted as meaning "including, without limitation," and the term "examples" is used to provide illustrative examples of the items under discussion, not an exhaustive or limiting list thereof.

[0086] Adjectives such as "conventional," "traditional," "usual," "standard," "known," and words of similar import should not be construed as limiting the items described to those available during a particular period or at a particular time, but should instead be construed as embracing conventional, traditional, ordinary, or standard technology that may be available or known now or at any time in the future. Similarly, when this patent application refers to technology that would be apparent or known to one of ordinary skill in the art, such technology includes technology that would be apparent or known to one of ordinary skill in the art now or at any time in the future.

[0087] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. The terms "a" or "an" should be interpreted to mean "at least one," "one or more," etc. In some cases, the presence of broader words or phrases such as "one or more," "at least," "but not limited to," or other similar phrases should not be interpreted to imply that the narrower case is intended or required when such broader phrases may not be present.

[0088] Materials, designs, synthesis methods, and devices related to fast-charging Li-ion batteries are provided in this disclosure. Fast-charging Li-ion batteries can include an anode, a cathode, an electrolyte, a separator, and a packet foil. Li-ion batteries can be charged in minutes instead of hours. The batteries can be one or more of pouch cells, cylindrical cells, button cells, prismatic cells, or other battery types.

[0089] The present invention fills a technology gap by providing an anode material having, in some variations, disordered rocksalt lithium vanadium oxide, achieving fast charging in less than 10 minutes, energy density in excess of 200 W·h / kg, a lifespan of at least 10,000 cycles, and improved battery safety.

[0090] In some embodiments, Li3V2O5 having a disordered rock salt structure can be implemented as an anode material where two lithium atoms can be reversibly inserted into Li3V2O5 to form Li5V2O5. In some embodiments, the anode material operates at a voltage of about 0.6 V. In some embodiments, the anode material undergoes little or no lithium coating during use, allowing for rapid charging, and Li4Ti5O 12 The present invention provides a lithium-ion battery having a cell voltage that is approximately 1 V higher than that of a conventional anode.

[0091] Some variations provide an anode material comprising a plurality of anode material particles, where the anode material particles comprise an internal phase comprising lithium vanadium oxide and a surface coating disposed on an outer surface of the internal phase, the lithium vanadium oxide being Li a V b O c (a=0.001 to 10, b=1 to 3, c=1 to 9, and a, b, and c are Li a V b O c (selected to balance the charge of Li a V b O c is capable of being reversibly lithiated, and the surface coating comprises a species selected from the group consisting of carbon, a metal oxide, a metalloid oxide, a metal fluoride, a metalloid fluoride, a metal phosphate, a metalloid phosphate, and combinations thereof.

[0092] Li a V b O c Non-integer values ​​of a, b, and c are possible as long as Li is charge balanced. a V b O c In some embodiments, a=0.001 to 5. a V b O c In various embodiments of the present invention, a is about, at least about, or at most about 0.001, 0.002, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 2.95, 3.0, 3.05, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, or 10.0.

[0093] Li a V b O c In some embodiments, b=1.5 to 2.5. a V b O c In various embodiments, b is about, at least about, or at most about 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.95, 2.0, 2.05, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0, including any range therebetween.

[0094] Li a V b O c In some embodiments, c=3 to 7. a V b O c In various embodiments, c is about, at least about, or at most about 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 4.6, 4.7, 4.8, 4.9, 4.95, 5.0, 5.05, 5.1, 5.2, 5.3, 5.4, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, or 9.0, including any range therebetween.

[0095] The surface coating is Li a V b O c In order to enhance the conductivity of Li a V b O c In order to improve the interface stability of a V b O c The present invention may be used to reduce electrolyte penetration into the substrate, and / or for other purposes.

[0096] In some embodiments, the surface coating comprises carbon. The carbon may be predominantly sp type, predominantly sp 2 Type, or mainly sp 3In some embodiments, the carbons may be of the sp carbon and sp carbon. 2 Carbon combinations, sp carbon and sp 3 Carbon combination, sp 2 Carbon and sp 3 Combinations of carbons, or sp carbons, sp 2 Carbon and sp 3 It is a combination of carbon.

[0097] In some embodiments, the surface coating comprises a metal oxide and / or a metalloid oxide. Exemplary oxides include, but are not limited to, TiO2, ZnO, Al2O3, B2O3, SiO2, MgO, Y2O3, ZrO2, WO3, or combinations thereof. In this disclosure, metalloids include B, Si, Ge, As, Sb, Te, and Po.

[0098] In some embodiments, the surface coating comprises a metal fluoride and / or a metalloid fluoride. Exemplary fluorides include, but are not limited to, MgF2, AlF3, ZnF2, LiF, SiF4, or combinations thereof.

[0099] In some embodiments, the surface coating comprises a metal phosphate and / or a metalloid phosphate. Exemplary phosphates include, but are not limited to, (Mg)3(PO4)2, AlPO4, Li3PO4, Si3(PO4)4, or combinations thereof.

[0100] In some embodiments, the surface coating comprises (a) carbon and (b) a metal oxide and / or a metalloid oxide. In some embodiments, the surface coating comprises (a) carbon and (b) a metal fluoride and / or a metalloid fluoride. In some embodiments, the surface coating comprises (a) carbon and (b) a metal phosphate and / or a metalloid phosphate. In some embodiments, the surface coating comprises (a) a metal oxide and / or a metalloid oxide and (b) a metal fluoride and / or a metalloid fluoride. In some embodiments, the surface coating comprises (a) a metal oxide and / or a metalloid oxide and (b) a metal phosphate and / or a metalloid phosphate. In some embodiments, the surface coating comprises (a) a metal fluoride and / or a metal fluoride and (b) a metal phosphate and / or a metalloid phosphate. In certain embodiments, the surface coating comprises three of: (a) carbon, (b) metal oxides and / or metalloid oxides, (c) metal fluorides and / or metalloid fluorides, and (d) metal phosphates and / or metalloid phosphates. In certain embodiments, the surface coating comprises all of: (a) carbon, (b) metal oxides and / or metalloid oxides, (c) metal fluorides and / or metalloid fluorides, and (d) metal phosphates and / or metalloid phosphates.

[0101] When the surface coating includes carbon, the carbon can be in the form of graphene, graphite, carbon nanotubes, carbon fibers, fullerenes, ultrafine carbon, carbon black, nanodiamonds, hard carbon, soft carbon, or combinations thereof. The carbon can generally be amorphous, crystalline, semi-crystalline, or combinations thereof.

[0102] The surface coating may be continuous or discontinuous on the surface of the lithium vanadium oxide. The surface coating may be completely solid or porous. The surface coating may have a thickness ranging from nanometer thickness to micron level thickness. The thickness of the coating may be uniform or non-uniform across the surface. The surface coating may be a single layer or may be a multi-layer coating.

[0103] FIG. 1 is a schematic diagram of carbon-coated VO 100 and carbon-coated disordered rock salt lithium vanadium oxide (DRS-LVO) 150 in some embodiments of the present invention. Carbon-coated VO 100 includes an internal phase 110 including VO and a coating 120 including carbon. Carbon-coated disordered rock salt lithium vanadium oxide 150 includes an internal phase 160 including lithium vanadium oxide (e.g., Li VO ) and a coating 170 including carbon. Coating 170 may be compositionally and / or structurally the same as coating 120, or the coatings may be different, in which case lithiation of VO alters the carbon coating. In this disclosure, "lithiation" refers to the incorporation of at least one lithium atom into a material.

[0104] In some embodiments, the surface coating has an average coating thickness selected from about 0.1 nanometers to about 100 nanometers. In various embodiments, the surface coating has an average coating thickness of about, at least about, or at most about 0.1, 0.2, 0.5, 1, 1.5, 2, 2.5, 3, 4, 5, 10, 15, 25, 50, 75, or 100 nanometers, including any range therebetween.

[0105] In some embodiments, the anode material particles have a shape selected from the group consisting of spherical, cylindrical, cubic, irregular, and combinations thereof. The anode material particles can have an average effective diameter selected from, for example, about 0.01 microns to about 100 microns. In various embodiments, the average effective diameter of the anode material particles is about, at least about, or at most about 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 1, 1.5, 2, 2.5, 3, 4, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, or 100 microns, including any range therebetween. The anode material particles can have a unimodal or multimodal size distribution.

[0106] In some embodiments, the surface coating is a non-porous coating that is free of voids. In other embodiments, the surface coating is a porous coating. The surface coating can have an average porosity selected from, for example, about 1% to about 95%. In various embodiments, the surface coating has an average porosity of about, at least about, or at most about 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%, including any range therebetween.

[0107] In some embodiments, the anode material is characterized as being chemically stable in the presence of air, as determined in this disclosure at atmospheric pressure (1 bar) and room temperature (25° C.) for a period of at least one day, preferably at least one week, and more preferably at least one month.

[0108] In some cases, the anode material is characterized as being chemically stable in the presence of water, which in the present disclosure is determined upon immersion in water at atmospheric pressure (1 bar) and room temperature (25° C.) for at least 1 hour, preferably at least 2 hours, and more preferably at least 3 hours.

[0109] Preferably, Li a V b O c At least 10% by weight of

number

number

number

number

number

[0110] The disordered rock salt structure is described in Liu et al., "A disordered rock salt anode for fast-charging lithium-ion batteries," Nature volume 585, pages 63-67 (2020), which is incorporated herein by reference. The disordered rock salt crystal structure is

number

[0111] Disordered rock salt crystal structures are in contrast to ordered rock salt crystal structures, such as NaCl, where sodium and chloride ions form a regular, ordered structure. In disordered rock salt crystal structures, the exact positions of the metal ions vary, but the overall crystal structure still exists. This specification incorporates by reference International Tables for Crystallography Volume A: Space-group symmetry, Second online edition, edited by Aroyo, 2016.

[0112] The disordered rock salt crystal structure also contrasts with disordered amorphous structures that lack a crystal lattice. For example, Li a V b O c In the case of Li3V2O5, nominally, an amorphous structure means that the Li, V, and O atoms are randomly arranged within the material, randomly bonded to each other, and do not form crystals. Crystalline solids have well-defined edges and faces, tend to diffract X-rays, and have sharp melting points. In contrast, amorphous solids have irregular or curved surfaces, do not produce X-ray diffraction patterns with sufficient resolution, and melt over a wide range of temperatures. In the present invention, Li a V b O c is preferably crystalline or has a crystallinity of at least 80%, at least 85%, at least 90%, at least 95%, at least 99% or 100%. Li having a crystallinity of at least 80% a V b O cis referred to herein as crystalline LVO, or c-LVO. The crystallinity of LVO can be measured using X-ray diffraction.

[0113] Lithium-free a V b O c The precursor - typically vanadium pentoxide, V2O5 - itself can be crystalline or amorphous. In principle, the disordered rock salt structure will remain until at least one lithium atom is inserted into V2O5 (i.e., Li a V b O c During lithiation, as the value of a increases, it is preferred that the rock salt structure be maintained, even at very high values ​​of a, such as 4, 5, or even greater. For example, in a preferred embodiment, the disordered rock salt structure is maintained through the conversion of Li3V2O5 to Li4V2O5 or Li5V2O5. During lithiation, the initial formation of a disordered rock salt structure by the introduction of lithium atoms is followed by Li3V2O5 having a disordered rock salt crystal structure. a V b O c In another embodiment, the proportion of Li having a disordered rock salt crystal structure may be further increased. a V b O c The ratio of Li to Li remains relatively constant as the degree of lithiation (value of a) increases. In certain embodiments, upon first discharge, a V b O c may indicate a superstructure in the rock-salt lattice that disappears upon further cycling. The disappearance of the superstructure does not affect the disordered rock-salt structure and electrochemical performance.

[0114] Li a V b O c can exist in a prelithiated state, in which case Li a V b O c During use of the anode material, and in some cases before use, Li a V b Oc exists in a lithiated state, in this case Li a V b O c where a>0.

[0115] Li a V b O c Li3V2O5, Li4V2O5, Li5V2O5, LiV2O5, Li 0.001 V2O5, Li2V2O5, Li 0.001 VO2, LiVO2, Li2VO2, Li 0.001 VO3, LiVO3, Li2VO3, Li3VO3, Li 0.001 V3O8, LiV3O8, Li2V3O8, Li3V3O8, Li 0.001 V2O3, LiV2O3, Li2V2O3, Li3V2O3, and combinations thereof.

[0116] Li a V b O c is about 1.5g / cm 3 to about 5.5 g / cm 3 In various embodiments, the Li a V b O c is about, at least about, or at most about 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.35, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, or 5.5 g / cm, including any range therebetween. 3 has a density of

[0117] In some embodiments, the lithium vanadium oxide is a compound having a composition of Li a V b O c M d(a=0.001-10, b=1-3, c=1-9, and d=0.001-3, where a, b, c, and d are the a V b O c M d The lithium vanadium oxide further comprises a dopant M chemically or physically contained within the lithium vanadium oxide, the dopant M being provided by a charge balance of Li a V b O c M d can be reversibly lithiated. a V b O c M d is a stoichiometric convenience and does not necessarily mean that the dopant M is chemically bound to any other species present.

[0118] The dopant M can be selected from the group consisting of, for example, Be, Mg, Ca, Zn, Fe, Cu, Sc, B, Y, Al, La, Si, Ge, Sn, Ti, Zr, Mn, P, Nb, Ta, Cr, Mo, W, Se, and combinations thereof. The dopant can include one or more divalent, trivalent, tetravalent, pentavalent, or hexavalent dopants. The multiple dopants can include Li a V b O c M d In this case, each dopant in the empirical formula may have d=0.1-3.

[0119] Dopants can be used to modify the properties of the lithium vanadium oxide, for example, to adjust the lithiation, delithiation, or other kinetics, the lithiation capacity, the anode stability, the lithiation-delithiation potential, the electronic conductivity of the anode material, the lithium ion diffusivity in the crystal structure of the anode material, and / or other factors.

[0120] In some embodiments, the surface-coated Li a V b Oc represents a base composition to which a dopant can be added. The doped composition can have a disordered rock salt structure. The dopant element may or may not be incorporated into the disordered rock salt crystal lattice. That is, when a dopant M is present, in some embodiments, Li a V b O c M d is a crystal lattice that includes a disordered arrangement of Li, V, and M atoms at cation lattice sites. Alternatively or additionally, the dopant M may be in a different position, such as randomly located, within the cation lattice of the disordered rock salt crystal structure, or may be in a different crystal lattice that governs the relationship of M to other atoms, potentially superimposed onto the disordered rock salt crystal structure. In certain embodiments, the presence of the dopant M reduces the optimal amount of vanadium (the value of b) in the disordered rock salt anode material.

[0121] Li a V b O c M d (doped anode material) is approximately 1.5 g / cm 3 to about 4.5 g / cm 3 Preferably, the density of Li a V b O c M d At least 50% by weight or at least 90% by weight of

number

number

[0122] Doped lithium vanadium oxide, Li a V b O c M d may comprise a surface coating selected from the group consisting of: (a) carbon, (b) metal oxides and / or metalloid oxides, (c) metal fluorides and / or metalloid fluorides, (d) metal phosphates and / or metalloid phosphates, and combinations thereof.

[0123] Disordered rock salt Li a V b O c Or Li a V b O c M d The source of vanadium oxide can be of various initial purities, such as V2O5 (vanadium pentoxide), low grade material of less than 98% V2O5 by weight, medium grade material of 98-99% V2O5 by weight, or high grade material of more than 99% V2O5 by weight. The V2O5 can be monocrystalline, polycrystalline, or amorphous. The V2O5 can be in the form of a hydrate. The particle size of the V2O5 (or other vanadium oxides such as VO, VO2, or V2O3) can be, for example, from about 0.2 microns to about 100 microns and can have a narrow, medium, or wide size distribution or a multimodal size distribution. The vanadium oxide particles can be spherical, cylindrical, cubic, flaky, irregular, or a mixture of various shapes.

[0124] If a dopant is utilized, the dopant may be incorporated following lithiation, i.e., the dopant is Li a V b O c Li is added to a V b O c M d Alternatively or additionally, a dopant can be incorporated into V2O5 prior to lithiation to form a doped vanadium oxide, V b O c M d(b=1-3, c=1-9, and d=0.001-3). The doped vanadium oxide can be formed by adding less than 98% by weight of V. b O c M d Low grade material, 98-99% V by weight b O c M d Medium grade materials or >99% by weight V b O c M d High grade materials may be used. b O c M d can be monocrystalline, polycrystalline, or amorphous. b O c M d The particle size of the doped vanadium oxide V can be, for example, from about 0.2 microns to about 100 microns, and can have a narrow, medium, or wide size distribution, or a multimodal size distribution. b O c M d The particles can be spherical, cylindrical, cubic, flaky, irregular, or a mixture of different shapes.

[0125] Particle size can be measured by a variety of techniques, including, for example, dynamic light scattering, laser diffraction, or image analysis. Dynamic light scattering is a non-invasive, established technique for measuring particle size and size distribution, typically in the submicron range, with the latest techniques measuring down to one nanometer. Laser diffraction is a widely used particle size technique for materials ranging in size from hundreds of nanometers to several millimeters. Exemplary dynamic light scattering and laser diffraction instruments for measuring particle size are available from Malvern Instruments Ltd., Worcestershire, UK. Image analysis to estimate particle size and particle distribution can be performed directly on photomicrographs, scanning electron micrographs, or other images.

[0126] Exemplary specifications for vanadium oxide or doped vanadium oxide are as follows: ·Purity: More than 99.0% by weight Average particle size: 3~5μm ·Crystal density: 3.36g / cm 3 Tap density: 2.5g / cm 3 Super.

[0127] Exemplary specifications for lithium vanadium oxide or doped lithium vanadium oxide as the anode material are as follows: ·Purity: More than 99.0% by weight Average particle size: 3~5μm ·Crystal density: 3.95g / cm 3 Tap density: 2.8g / cm 3 Super Li / Li + Nominal voltage for: 0.59V Nominal capacity at 0.5C: >225mA·h / g Capacity at 20℃: over 150mA·h / g First cycle efficiency: >90% Maximum charging voltage: Li / Li + 2.0V for ·Maximum charging current: 100C Discharge cutoff voltage: Li / Li + 0.01V ·Maximum discharge current: 100C.

[0128] Discharge current can be expressed as a C-rate to normalize it to the battery capacity. The C-rate is a measure of how fast a battery is discharged relative to the battery's maximum capacity. A 1C rate means that the discharge current will discharge the battery in 1 hour. For a battery with a capacity of 10A·h (ampere-hours), this corresponds to a discharge current of 10A (amperes). A 20C rate for this battery would be 200A and a C / 2 rate would be 5A.

[0129] In some embodiments, the anode material further comprises one or more additional anode material components selected from the group consisting of silicon, silicon oxide, tin, tin oxide, phosphorus, carbonaceous species, and combinations thereof, where the carbonaceous species is different from the carbon (if any) contained in the surface coating. The carbonaceous species can be graphite, non-graphitized carbon, hard carbon, soft carbon, or combinations thereof. The additional anode material components collectively can range, for example, in a total concentration of about 0.25% to about 99.75% by weight of the anode. In various embodiments, the additional anode components collectively have a total concentration of about, at least about, or at most about 0.25%, 0.5%, 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 97%, 98%, 99%, 99.5%, or 99.75% by weight, including any range therebetween.

[0130] The anode material may, for example, be about 1.5 g / cm 3 to about 5.0 g / cm 3 In various embodiments, the anode material can have a density of about, at least about, or at most about 1.5 g / cm, including any range therebetween. 3 , 2.5g / cm 3 , 3.0g / cm 3 , 3.5g / cm 3 , 4.0g / cm 3 , 4.5g / cm 3 , or 5.0 g / cm 3 has a density of

[0131] The anode material can have a volume porosity selected from, for example, about 5% to about 80% of the anode material. In various embodiments, the anode material has a volume porosity of about, at least about, or at most about 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, or 80% of the anode material, including any range therebetween.

[0132] In a preferred embodiment, Li a V b O c is the amount of Li a V b O c undergoes a volume change of about 0% to about 20%. Preferably, Li a V b O c The volume change of Li during one lithiation-delithiation cycle is about 0% to about 10%, and more preferably about 0% to about 5%. a V b O c undergoes a volume change of about, or at most about, 0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, or 20%, including any range therebetween.

[0133] Some variations of the present invention provide anodes that include the disclosed anode materials.

[0134] The anode may further comprise one or more additional anode components selected from the group consisting of silicon, silicon oxide, tin, tin oxide, phosphorus, carbonaceous species, and combinations thereof, where the carbonaceous species is different from the carbon (if any) contained in the surface coating. The additional anode components may collectively range, for example, from about 0.25% to about 97% total concentration by weight of the anode. In various embodiments, the additional anode components collectively have a total concentration of about, at least about, or at most about 0.25%, 0.5%, 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or 97% by weight, including any range therebetween.

[0135] When the anode comprises a carbonaceous species, the carbonaceous species can be graphite, non-graphitized carbon, hard carbon, soft carbon, or a combination thereof. The carbonaceous species can be useful as a conductive additive to improve the cell's rate performance and the cell's energy density. The conductive carbon additive can include one or more of carbon nanotubes, carbon black, carbon fibers (e.g., vapor-grown carbon fibers), ultrafine carbon, graphene, graphite, hard carbon, soft carbon, or other carbon additives.

[0136] In some embodiments, the anode further comprises one or more binders. The binder can hold the anode active materials together as well as place the anode active materials in contact with the anode substrate (e.g., copper foil). The binder can also help to keep the conductive carbon additive in place relative to the active materials.

[0137] The binder may be, for example, an aqueous binder selected from the group consisting of carboxymethyl cellulose, styrene-butadiene rubber, styrene-butadiene copolymer, polyacrylic acid, lithium substituted polyacrylic acid, and combinations thereof. Alternatively or additionally, the binder may be, for example, a non-aqueous binder selected from the group consisting of polyvinylidene fluoride, poly(vinylidene fluoride-co-hexafluoropropylene), and combinations thereof.

[0138] The concentration of the binder can range, for example, from about 0.25% to about 50% by weight of the anode. In various embodiments, the binder collectively has a total concentration of about, at least about, or at most about 0.25%, about 0.5%, about 1%, about 2%, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 40%, about 50%, about 60%, about 70%, or about 80% by weight, including any range therebetween.

[0139] In some embodiments, the anode further comprises an additional source of lithium beyond that provided by the lithium vanadium oxide, which can be, for example, pure lithium (Li) or lithiated carbon (e.g., LiC6).

[0140] In some embodiments, the anode has a volumetric anode porosity selected from about 5% to about 80%. In various embodiments, the anode has a volumetric anode porosity of about, at least about, or at most about 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, or 80%, including any range therebetween.

[0141] In some embodiments, the anode has an average anode thickness of about 100 nanometers to about 500 microns. In various embodiments, the anode has an average anode thickness of about, at least about, or at most about 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 1 μm, 2 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 200 μm, 300 μm, 400 μm, or 500 μm, including any range therebetween.

[0142] The anode can be in a cell, which is an electrochemical cell that can produce electrical energy from a chemical reaction or use electrical energy to drive a chemical reaction.

[0143] The cell may further include a cathode, a separator, and a packet foil surrounding the anode, separator, and cathode, where the separator is configured to electrically isolate the anode from the cathode. The anode composite may be disposed on a first substrate (e.g., copper foil) to form the anode, and the cathode composite may be disposed on a second substrate (e.g., aluminum foil) to form the cathode. In a layered cell configuration, there may be multiple layers of anodes, separators, and cathodes. The layers are repeatedly stacked to form a multi-layer stack in the cell configuration, forming anode, separator, cathode, separator, anode, separator, cathode, separator, etc., depending on the total number of layers.

[0144] In some embodiments, the anode has a loading of anode material selected from about 20% to about 100% by weight, for example, about 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100% by weight, including any range therebetween.

[0145] In some embodiments, the anode has a concentration of about 0.2, 0.5, 1, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 mg / cm, including any range therebetween, on at least one side of the anode (e.g., on both sides of the anode). 2 and so forth, about 0.2 mg / cm on at least one side of the anode. 2 ~about 50mg / cm 2 The surface load of the anode material is selected from:

[0146] In some embodiments, the anode has a current density of about 0.05, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mA·h / cm, including any range therebetween, on at least one side of the anode (e.g., on both sides of the anode). 2 and approximately 0.05 mA·h / cm on at least one side of the anode. 2 ~Approx. 10mA h / cm 2 The anode material has an areal capacity selected from:

[0147] In some embodiments, the anode has a capacity in the range of about 50 mA·h / g to about 500 mA·h / g, such as about 50, 100, 150, 200, 250, 300, 350, 400, 450, or 500 mA·h / g, including any range therebetween.

[0148] In some embodiments, the anode has a negative to positive electrode ratio (N / P ratio) ranging from about 0.5 to about 1.5, such as about 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5, including any range therebetween.

[0149] Copper foil, or other metal foil, can be used as a substrate upon which the anode material is disposed. In some embodiments, the thickness of the copper foil can range from about 1 μm to about 100 μm, such as about 1, 5, 10, 20, 30, 40, or 50 μm, including any range therebetween. In some embodiments, the press density of the anode can be about 0.3, 0.4, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5 g / cm, including any range therebetween. 3 etc., about 0.3g / cm 3 ~About 5g / cm 3 The range may be:

[0150] When the anode material is disposed on a substrate, the anode material is typically disposed on both sides of the substrate layer. This is called a bilayer. Within a cell, the number of bilayers can vary widely, such as from 1 to about 50, for example, about 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, or more.

[0151] The anode material can facilitate charging of Li-ion batteries in minutes without complex nanosizing processes. The anode material can enable fast charging batteries without sacrificing energy density. In some embodiments, the anode material can exhibit a voltage plateau in the range of about 0V to about 2V. In some embodiments, the voltage plateau can be about 0.6V, e.g., about 0.55V, about 0.56V, 0.57V, 0.58V, 0.59V, 0.60V, 0.61V, 0.62V, 0.63V, or 0.64V. The range of voltage potential can ensure that under high current, the anode potential achieves a value that does not cause lithium plating. The range of voltage potential can also ensure that the average cell voltage does not drop below about 1.5V when a common cathode material is used.

[0152] As mentioned above, the cell can include a cathode. The cathode can be LiFePO4, LiMn2O4, LiNi 0.5 Mn 1.5 O4, LiNi x Co y Mn z O2(x+y+z=1), LiCoO2, LiNi x Co y Al z O2(x+y+z=1), LiFe x Mn y PO4(x+y=1), aLiNi x Co y Mn z The cathode may include a cathode material selected from the group consisting of O2·(1-a)Li2MnO3 (where a=0-1 and x+y+z=1), and combinations thereof. Other cathode materials may be utilized. The cathode may be combined with an anode based on the composition of each electrode.

[0153] In some embodiments, the cathode can have a capacity ranging from about 50 mA·h / g to about 400 mA·h / g, for example. In some embodiments, the loading of the cathode active material can range from about 50% to about 100% by weight. In some embodiments, the coating weight on each side of the cathode can be about 0.5 mg / cm 2 ~about 30mg / cm 2 In some embodiments, the areal capacitance of each side of the cathode can range from about 0.2 mA·h / cm 2 ~Approx. 10mA h / cm 2 The range may be:

[0154] In some embodiments, the cathode has a press density of about 0.3 g / cm 3 ~About 5g / cm 3 The thickness of the aluminum foil may range from about 1 μm to about 100 μm. The number of cathode bilayers may range from 1 to about 50, for example. Aluminum foil may be used as a substrate for disposing the cathode material. In some embodiments, the thickness of the aluminum foil may range from about 1 μm to about 100 μm.

[0155] In some embodiments, the cell further comprises an electrolyte. The electrolyte may be selected from a liquid electrolyte (including a non-aqueous electrolyte or an aqueous electrolyte), a polymer gel electrolyte, a solid electrolyte, an ionic liquid, or a combination thereof. The electrolyte may be used to fill the separator to facilitate the movement of ions between the cathode and the anode during charging and discharging. During charging, lithium ions move from the cathode to the anode, while during discharging, lithium ions move from the anode to the cathode.

[0156] Examples of solvents that can be used in the electrolyte include, but are not limited to, propylene carbonate, ethylene carbonate, butylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propionate, fluoroethylene carbonate, dimethoxyethane, bis(2,2,2-trifluoroethyl)ether, γ-butyrolactone, methyl formate, methyl acetate, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formaldehyde, ethyl ketone ... amide, dimethylformamide, dioxolane, dioxane, acetonitrile, nitromethane, ethyl monoglyme, phosphate triester, trimethoxymethane, dioxolane derivatives, sulfolane, 3-methyl-2-oxazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ethyl ether, 1,3-propane sultone, N-methylacetamide, acetonitrile, acetals, ketals, sulfones, sulfolane, aliphatic ethers, cyclic ethers, glymes, polyethers, phosphate esters, siloxanes, dioxolanes, and N-alkylpyrrolidones.

[0157] The electrolyte may further include lithium salts such as LiPF6, LiClO4, LiBF4, LiAsF6, LiCF3SO3, LiCF3CO2, LiN(FSO2)2, LiN(CF3SO2)2, LiBF2(C2O4), LiB(C2O4)2, LiPO2F2, LiSbF6, LiAlCl4, LiCl, LiBr, and LiI, or other salts, or combinations thereof. Other minor components and impurities may be present in the electrolyte as known in the art.

[0158] In some embodiments, the electrolyte can have an electrolyte capacity value ranging from about 0.5 g / A·h to about 10 g / A·h, hi various embodiments, the electrolyte has an electrolyte capacity value of about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 g / A·h, including any range therebetween.

[0159] The separator electrically insulates the cathode from the anode. The separator may be non-conductive or may have low conductivity. The separator may be made of one or more of natural or synthetic rubber, glass fiber, cellulose, nanocellulose, polyolefin (e.g., polyethylene or polypropylene), or other materials. The separator may be porous to retain the electrolyte. In some embodiments, the pore size of the separator ranges from about 10 nm to about 150 nm. The separator may be made to close the pores when the temperature exceeds a threshold value to prevent the reaction from increasing. In some embodiments, the thickness of the separator ranges from about 5 μm to about 50 μm. In some embodiments, the porosity of the separator ranges from about 30% to about 70%. In some embodiments, the separator is coated with another material that closes across the pores to prevent overheating.

[0160] The packet foil insulates the anode-separator cathode assembly from the external environment. The packet foil can be made of polymers such as polyamide, polyester-polyurethane, polypropylene, and / or metals such as aluminum. The thickness of the packet foil can range from about 20 μm to about 200 μm.

[0161] Exemplary methods of making and using lithium vanadium oxide are further described below. Disordered rock salt LVO can be prepared, for example, via wet chemical synthesis and / or in situ electrochemical methods.

[0162] FIG. 2 is a schematic diagram of the chemical synthesis of disordered rock salt lithium vanadium oxide from starting V2O5 powder according to some embodiments of the present invention. As shown in FIG. 2, the starting V2O5 powder can be dispersed and stirred in a liquid lithiation reactant. The V2O5 powder can be sourced from a vanadium deposit and can be further ground to a desired particle size. The V2O5 powder can be coated with carbon to enhance its electronic conductivity and / or can be coated with another material as described above. The V2O5 powder can be doped with one or more dopants. The lithiation reactant can be a lithium-containing organic compound dissolved in a solvent, such as n-butyl lithium (LiC4H9) in hexane solution or lithium naphthalene (LiC4H9) in tetrahydrofuran (THF). 10 H8). The lithiation reactant can be Li + into V2O5 and reduce V2O5 to form the disordered rock salt Li3V2O5. In the case of lithium naphthalene, the reaction is: V2O5+3LiC 10 H8→Li3V2O5+3C 10 H8.

[0163] FIG. 3 is a schematic diagram of an in situ electrochemical reaction for synthesizing disordered rocksalt lithium vanadium oxide from V2O5 according to some embodiments of the present invention. As shown in FIG. 3, starting V2O5 powder can be mixed with carbon additives and binders and then cast in copper foil to form an anode. Lithium metal is pressed onto the V2O5 electrode. V2O5 powder can be sourced from vanadium deposits and can be further ground to a desired particle size. V2O5 powder can be coated with carbon to enhance its electronic conductivity and / or coated with another material as described above. V2O5 powder can be doped with one or more dopants. Lithium metal, as a foil or powder (or both), serves as a reductant and lithium source. The lithiation reaction occurs upon infusion of electrolyte. The electrolyte dissolves Li metal and transfers Li ions into V2O5 to form disordered rocksalt Li3V2O5.

[0164] Some variations of the present invention provide a method of synthesizing an anode material, the method comprising: (a) applying a reducing agent to a precursor material, the reducing agent comprising lithium, the precursor material comprising vanadium oxide, vanadium lithium oxide, or a combination thereof, thereby producing a reduced material; (b) introducing a surface coating onto the reduced material after and / or during step (a), the surface coating comprising a species selected from the group consisting of carbon, metal oxides, metalloid oxides, metal fluorides, metalloid fluorides, metal phosphates, metalloid phosphates, and combinations thereof; (c) recovering an anode material comprising a plurality of anode material particles, the anode material particles comprising an internal phase comprising lithium vanadium oxide and a surface coating disposed on an outer surface of the internal phase, wherein the lithium vanadium oxide is Li a V b O c (a=0.001 to 10, b=1 to 3, c=1 to 9, and a, b, and c are Li a V b O c (selected to balance the charge of Li a V b O c can be reversibly lithiated.

[0165] In some ways, Li a V b O c At least 10% by weight of

number

number

[0166] In some methods, the precursor material includes V2O5, LiV2O5, Li2V2O5, or a combination thereof. Typically, the precursor material contains less lithium than the desired anode material that will be formed by lithiation.

[0167] In some methods, the reducing agent is n-butyllithium (LiC4H9), lithium naphthalene (LiC 10 H8), Lithium Anthracenide (LiC 14 H9), and combinations thereof. In certain embodiments, the reducing agent is lithium naphthalene prepared by dissolving lithium in a solution comprising naphthalene and a solvent, where the solvent is selected from the group consisting of tetrahydrofuran, 1,2-dimethoxyethane, dimethyl carbonate, and combinations thereof. Lithium naphthalene has the chemical formula Li + C 10 H8 - LiC4H9 and other alkyl lithiums (linear, branched, or cyclic) can be considered as organic salts having the formula: 10 H8 or LiC 14 Other aromatic lithiums besides H9 can be utilized as reducing agents. Another example of an alkyllithium is methyllithium, LiCH3. Other reducing organolithium reagents can be used.

[0168] In some methods, the precursor material further comprises a dopant M. The dopant M may be selected from the group consisting of Be, Mg, Ca, Zn, Fe, Cu, Sc, B, Y, Al, La, Si, Ge, Sn, Ti, Zr, Mn, P, Nb, Ta, Cr, Mo, W, Se, and combinations thereof.

[0169] In some ways, Li a V b O cis characterized by undergoing a volume change of about 0% to about 20%, such as about 0% to about 10%, or about 0% to about 5%, during one lithiation-delithiation cycle.

[0170] In typical anode materials, the cell is repeatedly charged and discharged over multiple charge / discharge cycles, in which case Li a V b O c is reversibly lithiated and delithiated multiple times. The cell can be, for example, charged and discharged for at least 1000 cycles. In various embodiments, the number of charge / discharge cycles is, for example, 1, 2, 3, 4, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1500, 2000, 2500, 3000, 3500, 4000, 4500, or 5000, or even more.

[0171] When the cell undergoes at least one charge / discharge cycle, the lithium vanadium oxide material preferably has a volume change of 0% to about 20% during the charge / discharge cycle. In various embodiments, after one charge / discharge cycle, the lithium vanadium oxide material has a volume change of about, or at most about, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5.5%, 5%, 4.5%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5%, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, or 0.0%, including any range therebetween. In various embodiments, after 2, 3, 4, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 charge / discharge cycles, the vanadium lithium oxide material retains about, or at most about 20%, 19%, or 20% of its original capacity, including any range therebetween. 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5.5%, 5%, 4.5%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5%, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, or 0.0% volume change.

[0172] Some methods are Dissolving the precursor material (e.g., using H2O2) to form a sol-gel (preferably a homogenous sol-gel); mixing (e.g., magnetic stirring) a precursor of the surface coating with the sol-gel to form a homogenous mixture; drying the homogenous mixture (e.g., in an oven), thereby forming a dry powder; calcining the dried powder in air, whereby the precursor of the surface coating is converted to the surface coating; recovering the anode material particles; and Further includes:

[0173] When the surface coating of step (b) contains carbon, the carbon may be of the sp type, sp 2 Type and / or sp 3 The carbon can be in the form of graphene, graphite, carbon nanotubes, carbon fibers (e.g., vapor-grown carbon fibers), ultrafine carbon, carbon black, nanodiamonds, hard carbon, soft carbon, or combinations thereof.

[0174] In some methods, the precursor material has a precursor material shape selected from the group consisting of spherical, cylindrical, cubic, irregular, and combinations thereof.

[0175] In some methods, the precursor material has an average effective diameter selected from about 0.1 microns to about 100 microns. The precursor material may have a bimodal particle size distribution.

[0176] In some methods, the precursor material is V2O5. V2O5 can be present in the precursor material in a purity range of, for example, about 90% to about 100% by weight.

[0177] The precursor materials can be dissolved using hydrogen peroxide (H2O2) or another suitable compound to form a sol-gel.

[0178] The surface coating can have an average coating thickness selected from, for example, about 0.1 nanometers to about 100 nanometers. The surface coating can have an average porosity selected from, for example, about 0% to about 95%.

[0179] The anode material can have a volume porosity of the anode material selected, for example, from about 5% to about 80%.

[0180] The method may further include introducing one or more additional components to the anode material, optionally selected from the group consisting of silicon, silicon oxide, tin, tin oxide, phosphorus, carbonaceous species, and combinations thereof, where the carbonaceous species is different from the carbon (if any) contained in the surface coating.

[0181] The method may further include introducing into the anode one or more binders selected from the group consisting of carboxymethyl cellulose, styrene-butadiene rubber, styrene-butadiene copolymer, polyacrylic acid, lithium substituted polyacrylic acid, polyvinylidene fluoride, and combinations thereof.

[0182] In some methods, the anode material is cast onto a first substrate to form a lithiated anode. The cathode material can be cast onto a second substrate to form a cathode. A separator can be laminated to the lithiated anode, and the cathode can be laminated to the separator. A packet foil can be configured to surround the anode, separator, and cathode to form a cell.

[0183] In some methods, the lithiated anode has a loading of anode material selected from about 20% to about 100% by weight. In some methods, the lithiated anode has a loading of about 0.2 mg / cm on at least one side of the lithiated anode. 2 ~about 50mg / cm 2 In some methods, the lithiated anode has a surface loading of the anode material selected from about 0.05 mA·h / cm on at least one side of the lithiated anode. 2 ~Approx. 10mA h / cm 2 The anode material has an areal capacity selected from:

[0184] The method further comprises, following step (c), cycling Li a V b O cIn the lithiation-delithiation cycle, Li a V b O c preferably undergoes a volume change of about 0% to about 20%, more preferably about 0% to about 10%, and most preferably about 0% to about 5% during lithium-delithiation cycling.

[0185] Yet another variation of the present invention provides a method of manufacturing a cell, the method comprising the steps of: (a) casting an anode material onto a first substrate to form an anode, the anode material comprising a plurality of anode material particles, the anode material particles comprising an internal phase comprising lithium vanadium oxide and an optional surface coating disposed on an external surface of the internal phase, the lithium vanadium oxide being Li x V y O z (x=0 to 10, y=1 to 3, z=1 to 9, and x, y, and z are Li x V y O z (selected to maintain a charge balance of (b) applying a reducing agent to the anode material, the reducing agent comprising lithium, whereby Li a V b O c (a=0.001 to 10, b=1 to 3, c=1 to 9, and a, b, and c are Li a V b O c (selected to maintain charge balance of Li a V b O c can be reversibly lithiated; (c) optionally removing excess reducing agent (if any) from the lithiated anode material; and (d) casting a cathode material onto a second substrate to form a cathode; (e) laminating a separator to the anode; (f) laminating a cathode to the separator; (g) surrounding the anode, separator, and cathode with foil to form a cell; Includes.

[0186] Some methods of manufacturing cells use Li a V b O c At least 10% by weight of

number

number

[0187] In some methods of manufacturing the cell, a surface coating is present and disposed on the outer surface of the internal phase, where the surface coating comprises a species selected from the group consisting of carbon, metal oxides, metalloid oxides, metal fluorides, metalloid fluorides, metal phosphates, metalloid phosphates, and combinations thereof.

[0188] If a surface coating is present and contains carbon, the carbon may be sp 2 Type and / or sp 3 Exemplary forms of carbon include graphene, graphite, carbon nanotubes, carbon fibers, ultrafine carbon, carbon black, nanodiamond, hard carbon, soft carbon, or combinations thereof.

[0189] In some methods of manufacturing the cell, the anode material further comprises a dopant M, where the dopant M is optionally selected from the group consisting of Be, Mg, Ca, Zn, Fe, Cu, Sc, B, Y, Al, La, Si, Ge, Sn, Ti, Zr, Mn, P, Nb, Ta, Cr, Mo, W, Se, and combinations thereof.

[0190] The method of manufacturing the cell may further include introducing one or more additional components selected from the group consisting of silicon, silicon oxide, tin, tin oxide, phosphorus, carbonaceous species, and combinations thereof into the anode material, where the carbonaceous species, when present, is different from the carbon (if any) contained in the surface coating.

[0191] The method of manufacturing the cell may further include introducing into the anode one or more binders selected from the group consisting of carboxymethyl cellulose, styrene-butadiene rubber, styrene-butadiene copolymer, polyacrylic acid, lithium substituted polyacrylic acid, polyvinylidene fluoride, and combinations thereof.

[0192] Some methods of manufacturing cells use Li a V b O c is the amount of Li a V b O c However, the volume of the liquid crystal display device is changed by about 0% to about 20%, preferably by about 0% to about 10%, and more preferably by about 0% to about 5%.

[0193] In some methods of manufacturing the cell, the anode has a loading of anode material selected from about 20% to about 100% by weight.

[0194] In some methods of manufacturing the cell, the anode comprises about 0.2 mg / cm2 of carbon nanotube on at least one side of the anode. 2 ~about 50mg / cm 2 The surface load of the anode material is selected from:

[0195] In some methods of manufacturing the cell, the anode has a current density of about 0.05 mA·h / cm on at least one side of the anode. 2 ~Approx. 10mA h / cm 2 The anode material has an areal capacity selected from:

[0196] The method of manufacturing the cell may further include injecting an electrolyte into the cell.

[0197] In some methods of manufacturing the cell, the first substrate can be, for example, a copper foil having a thickness of about 1 micron to about 100 microns, and the second substrate can be, for example, an aluminum foil having a thickness of about 1 micron to about 100 microns.

[0198] Yet another variation of the present invention provides a method of manufacturing a cell, the method comprising the steps of: (a) casting an anode material onto a first substrate to form an anode, the anode material comprising a plurality of anode material particles, the anode material particles comprising Li x V y O z (x=0 to 10, y=1 to 3, z=1 to 9, and x, y, and z are Li x V y O z an optional surface coating disposed on an outer surface of the internal phase; (b) pressing lithium into the anode to form a pressed anode; (c) casting a cathode material onto a second substrate to form a cathode; (d) laminating a separator onto the pressed anode; (e) laminating a cathode to a separator; (f) surrounding the plurality of anode layers, the plurality of separator layers, and the plurality of cathode layers with packet foil to form a dry cell; (g) injecting an electrolyte into the cell; and (h) Press the anode with Li a V b O c(a=0.001 to 10, b=1 to 3, c=1 to 9, and a, b, and c are the same as those described above.) a V b O c (selected to maintain charge balance of Li a V b O c can be reversibly lithiated; Includes.

[0199] In some embodiments, the anode is fabricated by mixing the active material, conductive carbon additive, and binder and pressing or calendaring into an electrode sheet without the use of a solvent (dry process). The anode can also be fabricated by mixing the active material, conductive carbon additive, and binder to form a slurry using water or a non-aqueous solvent and then casting the slurry onto a substrate (e.g., a current collector).

[0200] Some methods of manufacturing cells use Li x V y O z is V2O5. V2O5 may be present in the internal phase in an internal phase purity range of, for example, about 90% by weight to about 100% by weight.

[0201] In some methods of manufacturing the cell, the anode material particles have a shape of the anode material selected from the group consisting of spherical, cylindrical, cubic, irregular, and combinations thereof.

[0202] In some methods of manufacturing a cell, the Li formed in step (h) a V b O c At least 10% by weight of

number

number

[0203] In some methods of manufacturing the cell, a surface coating is present and disposed on the outer surface of the internal phase. The surface coating can include a species selected from the group consisting of carbon, metal oxides, metalloid oxides, metal fluorides, metalloid fluorides, metal phosphates, metalloid phosphates, and combinations thereof.

[0204] If a surface coating is present and contains carbon, the carbon may be sp 2 Type and / or sp 3 Exemplary forms of carbon include graphene, graphite, carbon nanotubes, carbon fibers, ultrafine carbon, carbon black, nanodiamond, hard carbon, soft carbon, or combinations thereof.

[0205] In some methods of manufacturing the cell, the anode material further comprises a dopant M, where the dopant M is optionally selected from the group consisting of Be, Mg, Ca, Zn, Fe, Cu, Sc, B, Y, Al, La, Si, Ge, Sn, Ti, Zr, Mn, P, Nb, Ta, Cr, Mo, W, Se, and combinations thereof.

[0206] Some methods of manufacturing the cell further include introducing one or more additional components to the anode material selected from the group consisting of silicon, silicon oxide, tin, tin oxide, phosphorus, carbonaceous species, and combinations thereof, where the carbonaceous species, when present, is different from the carbon (if any) contained in the surface coating.

[0207] Some methods of manufacturing the cell further include incorporating into the anode one or more binders selected from the group consisting of carboxymethyl cellulose, styrene-butadiene rubber, styrene-butadiene copolymer, polyacrylic acid, lithium substituted polyacrylic acid, polyvinylidene fluoride, and combinations thereof.

[0208] Some methods of manufacturing cells use Li a V b O c is the amount of Li a V b O c However, the volume of the liquid crystal display device is changed by about 0% to about 20%, preferably by about 0% to about 10%, and more preferably by about 0% to about 5%.

[0209] In some methods of manufacturing the cell, the anode comprises a loading of about 0.2 mg / cm of an anode material selected from about 20% by weight to about 100% by weight on at least one side of the anode. 2 ~about 50mg / cm 2 and a surface loading of the anode material selected from the group consisting of about 0.05 mA·h / cm on at least one side of the anode. 2 ~Approx. 10mA h / cm 2 The anode material has an areal capacity selected from:

[0210] In some methods of manufacturing the cell, step (b) does not utilize a solvent to form the pressed anode.

[0211] In some methods of manufacturing the cell, steps (g) and (h) are performed simultaneously rather than sequentially.

[0212] In some methods of manufacturing the cell, the first substrate is a copper foil having a thickness of, for example, about 1 micron to about 100 microns. Copper foil is a common anode current collector for Li-ion batteries. Copper foil is highly conductive and also dissipates heat generated by the battery. The anode material disposed on the copper foil can be referred to as "tape" or "anode tape". Other foil substrates can be used, and the foil can be modified, such as to enhance bonding with the foil or to adjust the conductivity.

[0213] In some methods of manufacturing the cell, the second substrate is an aluminum foil having a thickness of, for example, about 1 micron to about 100 microns. Aluminum foil is a common cathode current collector in Li-ion batteries.

[0214] In some variations, the method further includes casting an anode material onto a first substrate to form an anode, laminating a separator to the anode, the separator including an electrolyte, casting a cathode material onto a second substrate to form a cathode, laminating the cathode to the separator, and surrounding the anode, separator, and cathode with foil to form a cell. In a typical embodiment, there are multiple layers of anode, separator, and cathode in a cell.

[0215] In some embodiments, the disclosed technology can be used in a battery system that is superior to conventional graphite battery packs and has a smaller number of cells in the battery pack. The battery system can utilize any one (or more) of the disclosed anode materials and can be combined with a 4V high capacity cathode such as LiCoO2, Li-rich oxides, and / or Li(NiMnCo)O2 layered oxides. The battery system is suitable for many commercial applications such as electric vehicles, smart devices, and high power portable devices with high energy density.

[0216] The battery system can be safely operated over a wide temperature range, such as -30°C to 60°C.

[0217] The battery system may be rechargeable in about 30 minutes, 25 minutes, 20 minutes, 15 minutes, 10 minutes, 9 minutes, 8 minutes, 7 minutes, 6 minutes, 5 minutes, 4 minutes, 3 minutes, 2 minutes, or 1 minute, or about less, in various embodiments.

[0218] Those skilled in the art of battery technology will understand that battery design principles, including calculations, modeling, simulation, and engineering, may be implemented using the present disclosure and the benefit of the anode materials. Those skilled in the art of battery technology, with the benefit of this disclosure, will understand how to scale battery cell sizes to suit various battery applications.

[0219] In some embodiments of the invention, the anode material is made and then sent elsewhere for incorporation into an anode. In some embodiments of the invention, the anode (e.g., anode tape) is made and then sent elsewhere for incorporation into a cell. In some embodiments of the invention, the cell is made and then sent elsewhere for incorporation into a final device or vehicle. In some embodiments of the invention, the cell is made and then sent elsewhere for incorporation into a module. In some embodiments of the invention, the module is made and then sent elsewhere for incorporation into a final device or vehicle. In some embodiments of the invention, the cell is made and then sent elsewhere for incorporation into a pack. In some embodiments of the invention, the module is made and then sent elsewhere for incorporation into a pack. In some embodiments of the invention, the pack is made and then sent elsewhere for incorporation into a final device or vehicle.

[0220] There are many use cases for the present invention.

[0221] For wearable device and consumer electronics applications, for example, the battery capacity may range from 0.005 A·h to 15 A·h, the gravimetric energy density may range from 120 to 220 W·h / kg, the volumetric energy density may range from 250 to 650 W·h / L, the charging time may range from 10 seconds to 10 hours, and the cycle life may range from 50 to 100,000 cycles.

[0222] For robotics, micromobility, and power tool applications, for example, battery capacity may range from 1 to 20 A·h, gravimetric energy density may range from 150 to 220 W·h / kg, volumetric energy density may range from 350 to 650 W·h / L, charging time may range from 10 seconds to 10 hours, and cycle life may range from 50 to 100,000 cycles.

[0223] For electric vehicle and stationary energy storage applications, for example, the battery capacity may range from 2 to 250 A·h, the gravimetric energy density may range from 150 to 220 W·h / kg, the volumetric energy density may range from 350 to 650 W·h / L, the charging time may range from 10 seconds to 10 hours, and the cycle life may range from 50 to 100,000 cycles.

[0224] Table 1 is an exemplary cell design for a 221 A·h pouch cell. Table 2 is an exemplary cell design for a 25 A·h pouch cell. Table 3 is an exemplary cell design for a 2.3 A·h pouch cell. Table 4 is an exemplary cell design for a 0.44 A·h pouch cell.

[0225] [Table 1]

[0226] [Table 2]

[0227] [Table 3]

[0228] [Table 4] EXAMPLES

[0229] Working Example The following experiments were performed to demonstrate various embodiments of the disclosed technology. The experiments, data, and images are not intended to limit the scope of the invention in any way. In the drawings, "DRS" refers to disordered rock salt.

[0230] V2O5 powder with particle sizes of about 1 μm to about 20 μm was coated with carbon by physical ball milling with nanometer-sized Super P carbon. Figure 4 shows images of uncoated V2O5 and carbon-coated V2O5 taken using scanning electron microscopy (SEM). The morphology of V2O5 powder before and after ball milling with Super P carbon is revealed. Carbon particles cover the surface of V2O5 particles. As shown, nano-sized carbon adheres to the surface of V2O5 powder after mechanical treatment.

[0231] The morphology of the disordered rocksalt lithium vanadium oxide was investigated by scanning electron microscopy (SEM). Figure 5 shows SEM images of exemplary disordered rocksalt Li3V2O5 powders with various morphologies. Figure 5(a) shows that the primary particles of the disordered rocksalt lithium vanadium oxide aggregated to form spherical secondary particles with sizes ranging from about 5 μm to about 20 μm, with the primary particles ranging from about 200 nm to about 2 μm. Figure 5(b) shows that the primary particles of the disordered rocksalt lithium vanadium oxide aggregated to form large irregular agglomerates ranging from about 5 μm to about 50 μm, with the primary particles ranging from about 200 nm to about 2 μm. Figure 5(c) shows the disordered rocksalt lithium vanadium oxide in the form of flakes. The flake widths range from about 2 μm to about 10 μm, and the flake lengths range from about 5 μm to about 50 μm. Figure 5(d) shows single crystals of disordered rock-salt lithium vanadium oxide. The primary single crystal particles are well dispersed and range in size from about 200 nm to about 5 μm. These examples in Figures 5(a)-(d) show that the morphology of disordered rock-salt lithium vanadium oxide can be controlled.

[0232] Figure 6 shows the X-ray diffraction (XRD) graphs of disordered rock salt lithium vanadium oxides synthesized from V2O5 powder by various chemical methods. In Figure 6, the "Echem" lithium vanadium oxide was Li3V2O5 prepared by discharging a Li||V2O5 cell to 1.5 V. The "Chem-1" lithium vanadium oxide was the Li3V2O5 product of reacting V2O5 powder with n-butyl lithium (LiC4H9). The "Chem-2" lithium vanadium oxide was the Li3V2O5 product of reacting V2O5 powder with lithium naphthalene (LiC 10 H8) was reacted with Li3V2O5.

[0233] An example of the synthesis procedure is as follows. First, V2O5 and naphthalene are placed in a glass reactor in a molar ratio of 1:a (a=0.05-3). Second, tetrahydrofuran (THF) is added to the reactor as a solvent. The amount of THF is calculated so that the naphthalene concentration is in the range of 0.005-2 mol / L. When mechanically stirred, naphthalene can be dissolved in THF immediately. V2O5 powder is dispersed in the solution with orange color. Third, a stoichiometric amount of Li is fed into the solution while stirring. Li reacts with naphthalene, the color of the solution becomes dark blue, and V2O5 is immediately lithiated, and the color of the solution becomes black due to the dispersed LixV2O5. The reaction temperature can be controlled at room temperature or can be heated up to 80°C. The reaction period can range from 15 minutes to 24 hours. The reaction is under an inert atmosphere, i.e., under an atmosphere free of moisture and oxygen. Fourth, after reaction, the Li3V2O5 powder is filtered and washed with organic solvent, such as ethanol, THF, etc. The washed powder is filtered and dried under vacuum to obtain the final Li3V2O5. The drying temperature can range from room temperature to 200°C. The vacuum drying period can range from 15 minutes to 24 hours.

[0234] All lithium vanadium oxides in Figure 6

number

[0235] Figure 7 shows the XRD graph of the disordered rocksalt Li3V2O5 anode material prepared by in situ electrochemical reaction. The disordered rocksalt Li3V2O5 anode material was prepared by pressing a thin Li foil with a V2O5 electrode. A few drops of 1M LiPF6 in ethylene carbonate / ethyl methyl carbonate (volume ratio 3:7) electrolyte were placed between the V2O5 electrode and the Li foil to allow electrochemical lithiation. The XRD shows the pure disordered rocksalt Li3V2O5 structure on the Cu current collector. Figure 7 shows that the pure phase disordered rocksalt Li3V2O5 can be synthesized from V2O5 by in situ electrochemical reaction.

[0236] Figure 8 shows the charge / discharge voltage profiles of the Li3V2O5 anode material prepared by in situ electrochemical reaction. The disordered rock salt Li3V2O5 anode material was assembled into a coin cell. Using a current density of 100 mA / g, the charge / discharge voltage profiles were 0.01 V to 2 V in the first discharge, first charge, and second discharge, as shown in Figure 8. The initial discharge capacity was 307 mA·h / g. The average working potential was about 0.6 V, and the reversible capacity was 260 mA·h / g.

[0237] Figure 9 shows the XRD graphs of V2O5 and carbon-coated V2O5. To improve the electronic conductivity of V2O5 and its lithiated form, i.e., disordered rock salt Li3V2O5, a carbon coating layer was applied to the V2O5 powder. Glucose was used as the carbon source. The V2O5 powder was well dispersed in the glucose solution. The glucose-coated V2O5 powder was prepared by heating the solution to remove the water. The glucose-coated V2O5 powder was then calcined at 400-600 °C under nitrogen to form a nanocarbon coating layer on the surface of the V2O5. The XRD data in Figure 9 show that the carbon-coated V2O5 maintains the original pure phase structure of V2O5.

[0238] Figure 10 shows the XRD graphs of V2O5 and CNT (carbon nanotube) coated V2O5. V2O5 powder was dissolved with H2O2 to form a uniform sol-gel. Carbon nanotubes were added to the sol-gel under magnetic stirring to obtain a uniform mixture. The mixture was then dried in an oven to remove water. The dried powder was calcined at 350 °C in air for 2 h to form CNT coated V2O5. The XRD data in Figure 10 shows that the CNT coated V2O5 maintains the original pure phase structure of V2O5.

[0239] FIG. 11 shows the capacity retention of uncoated (bare) Li3V2O5 and CNT-coated disordered rock salt Li3V2O5 under various charge / discharge current rates. CNT-coated disordered rock salt Li3V2O5 was tested in a coin cell to evaluate its rate performance. As shown, CNT-coated disordered rock salt Li3V2O5 shows much higher capacity retention compared to uncoated disordered rock salt Li3V2O5. At 20C, i.e., 3 minutes of charging, CNT-coated disordered rock salt Li3V2O5 and bare disordered rock salt Li3V2O5 show 49% and 27% capacity, respectively, at a rate of 0.5C. The data in FIG. 11 shows that CNT-coated Li3V2O5 has better fast charging capability than uncoated Li3V2O5.

[0240] Figure 12 shows the cycling stability of the disordered rocksalt Li3V2O5 anode material after 50 cycles at a low temperature of -20°C. The disordered rocksalt Li3V2O5 was tested in a coin cell to evaluate its cycling performance at -20°C. As shown, the disordered rocksalt Li3V2O5 was very stable at -20°C with no capacity fade after 50 cycles.

[0241] FIG. 13 shows the cycling stability of the disordered rocksalt Li3V2O5 anode material after 25 cycles at high temperature of 60° C. The disordered rocksalt Li3V2O5 was tested in a coin cell to evaluate its cycling performance at 60° C. As shown, the disordered rocksalt Li3V2O5 was very stable at 60° C. with no capacity fade after 25 cycles.

[0242] Disordered rock salt Li3V2O5 to LiNi 0.8 Mn 0.1 Co 0.1 By combining it with O2 cathode material, complete cell performance was demonstrated. Figure 14 shows the charge / discharge voltage profile of an exemplary cell at various charge / discharge rates, demonstrating the fast charge capability. Figure 15 shows the cycling performance of the cell when cycled at a 5 min charge / discharge rate, demonstrating long-term stability. Notably, the cell delivered 45% capacity at a short charge of 2.5 min, demonstrating its fast charge capability. The cell also showed good cycling stability, maintaining a high capacity retention of about 92% for 1000 cycles at a 5 min charge / discharge rate. The cell performance data in Figures 14 and 15 show that the cell is stable at 1000 cycles for the disordered rock salt Li3V2O5||LiNi 0.8 Mn 0.1 Co 0.1 It demonstrates the fast charging capability and long-term stability of the O2 cell.

[0243] Figure 16 shows the XRD graphs of the disordered rocksalt Li3V2O5 prepared from V2O5 with various purities of 99.9 wt%, 99.5 wt%, and 98 wt% V2O5. As shown in Figure 16, the disordered rocksalt Li3V2O5 powders synthesized from V2O5 powders with various starting V2O5 purities all show pure disordered rocksalt phase in the Li3V2O5 anode material.

[0244] Disordered rock salt Li a V b O cThe Li concentration in the anode material can be controlled by adjusting the ratio of the lithiating agent to V2O5. For example, FIG. 17 demonstrates the successful synthesis of Li4V2O5 with a purely disordered rock salt structure. FIG. 17 shows the XRD graphs of the disordered rock salt Li3V2O5 and the disordered rock salt Li4V2O5 synthesized by wet chemical reaction. The (200) peak of the disordered rock salt Li4V2O5 is slightly to the left of the (200) peak of the disordered rock salt Li3V2O5, which is evidence of the higher lithium content of the disordered rock salt Li4V2O5 with 4 moles of lithium compared to the Li3V2O5 with 3 moles of lithium.

[0245] To evaluate the suitability of the disordered rocksalt lithium vanadium oxide in aqueous electrode slurry processing, the disordered rocksalt lithium vanadium oxide was immersed in water for 3 hours. Figure 18 is an XRD graph showing the water stability of the disordered rocksalt Li3V2O5. The XRD data of the immersed disordered rocksalt lithium vanadium oxide in Figure 18 shows a pure disordered rocksalt phase without any impurities. This result indicates that the disordered rocksalt lithium vanadium oxide is chemically stable in water.

[0246] The disordered rocksalt Li3V2O5 anode material was assembled into a coin cell with a Li metal counter electrode. Figure 19 shows the charge / discharge voltage profile of the disordered rocksalt Li3V2O5 between 0.01 V and 2 V at C / 2 rate (current density of 100 mA / g). The reversible capacity was 249 mA·h / g. The average working potential was about 0.58 V. This coin cell also showed excellent rate performance. Figure 20 shows the capacity retention of the disordered rocksalt Li3V2O5 at various charge / discharge current rates. As shown in Figure 20, at a high C rate of 20 C - a 3-minute charge - the disordered rocksalt Li3V2O5 showed 57% of its capacity at a rate of 0.5 C.

[0247] Figure 21 shows the XRD graphs of the disordered rocksalt Li3V2O5 in the charged and discharged states. The Li||disordered rocksalt Li3V2O5 battery was cycled between 0.01V and 2V. The cell was stopped at 0.01V and 2V, which correspond to the discharged and charged states, respectively. The material was collected from the disassembled battery. The XRD patterns in Figure 21 clearly show that the discharged and charged lithium vanadium oxide has a pure disordered rocksalt structure. The slight shift of the (200) peak of the vanadium lithium oxide suggests a small volume change of the disordered rocksalt Li3V2O5 during charging and discharging.

[0248] Disordered rock salt Li3V2O5 powder and conductive carbon were mixed with carboxymethyl cellulose (CMC)-water solution to form a slurry. The slurry was cast on copper foil and then dried to remove water. The dried electrode was calendered to form an anode sheet. The disordered rock salt Li3V2O5 anode was assembled into a coin cell with a Li metal counter electrode. Figure 22 shows the capacity retention of the disordered rock salt Li3V2O5 with CMC binder at various charge / discharge current rates. The specific capacity of the disordered rock salt Li3V2O5 was 233 mA·h / g at C / 2, and even at a charge / discharge rate of 10C, its specific capacity was 119 mA·h / g, more than 50% of the specific capacity at the C / 2 rate. Figure 23 shows the voltage profile of the disordered rock salt Li3V2O5 at various charge / discharge current rates of C / 2, 1C, 2C, 3C, 5C, and 10C.

[0249] The disordered rock-salt Li3V2O5 anode material was assembled into a coin cell with a Li metal counter electrode. The electrolyte was 1M LiPF6 in ethylene carbonate:ethyl methyl carbonate:dimethyl carbonate with a weight ratio of 3:5:2. Figure 24 shows the rate capability of the disordered rock-salt Li3V2O5 anode material in carbonate electrolyte and the capacity retention of the disordered rock-salt Li3V2O5 at various charge / discharge current rates. According to Figure 24, the disordered rock-salt Li3V2O5 anode material exhibited specific capacities of 260 mA·h / g, 247 mA·h / g, 232 mA·h / g, 224 mA·h / g, 210 mA·h / g, 188 mA·h / g, and 155 mA·h / g at charge / discharge rates of C / 2, 1C, 2C, 3C, 5C, 10C, and 20C, respectively. Figure 25 shows the voltage profiles of the disordered rock salt Li3V2O5 at various charge / discharge current rates (C / 2, 1C, 2C, 3C, 5C, 10C, and 20C). The average working potential was about 0.58 V.

[0250] The disordered rock-salt Li3V2O5 anode material was assembled into a coin cell with a Li metal counter electrode. The electrolyte was 1M LiPF6 in methylpropionate:fluoroethylene carbonate with a volume ratio of 9:1. Figure 26 shows the performance of the disordered rock-salt Li3V2O5 in an ester-based electrolyte and the capacity retention of the disordered rock-salt Li3V2O5 at various charge / discharge current rates. Figure 26 shows the rate capability and specific capacity of 290 mA·h / g, 278 mA·h / g, 261 mA·h / g, 253 mA·h / g, 236 mA·h / g, 206 mA·h / g, and 172 mA·h / g at charge / discharge rates of C / 2, 1C, 2C, 3C, 5C, 10C, and 20C, respectively. Figure 27 shows the voltage profile of the disordered rock-salt Li3V2O5 at various charge / discharge current rates. The average working potential was about 0.58 V. Figure 28 shows the long-term cycling performance of the disordered rock salt Li3V2O5. According to Figure 28, the disordered rock salt Li3V2O5 had negligible capacity change after 274 cycles at a rate of C / 2.

[0251] The disordered rock salt Li3V2O5 anode material was assembled into a coin cell with a Li metal counter electrode. The electrolyte was 2M LiFSI in 1,2-dimethoxyethane:bis(2,2,2-trifluoroethyl)ether with a weight ratio of 1:4. Figure 29 shows the performance of the disordered rock salt Li3V2O5 in ether-based electrolytes, showing the voltage profile of the disordered rock salt Li3V2O5 at various charge / discharge current rates. According to Figure 29, the anode material exhibited specific capacities of 271 mA·h / g, 245 mA·h / g, 228 mA·h / g, 220 mA·h / g, 208 mA·h / g, 190 mA·h / g, and 168 mA·h / g at charge / discharge rates of C / 2, 1C, 2C, 3C, 5C, 10C, and 20C, respectively. The average working potential was about 0.56 V. Figure 30 shows the cycling stability of the disordered rock salt Li3V2O5. The disordered rock salt Li3V2O5 surprisingly had negligible capacity change after 2250 cycles at a high C rate of 20C.

[0252] The Li||disordered rock salt Li3V2O5 battery was cycled at a temperature of 60°C for 50 cycles. The electrolyte was 1M LiPF6 in ethylene carbonate:ethyl methyl carbonate:dimethyl carbonate in a weight ratio of 3:5:2. After 50 cycles, the cell was disassembled at room temperature to test the stability of the disordered rock salt Li3V2O5 operated at high temperature (60°C). The counter electrode Li was examined by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). Figure 31 shows the SEM and energy dispersive X-ray spectroscopy (EDX) analysis of the Li metal counter electrode from the cycled Li||disordered rock salt Li3V2O5 at a temperature of 60°C. Figure 32 shows the EDX elemental analysis for C, O, F, and P of the Li metal counter electrode from the cycled Li||disordered rock salt Li3V2O5 at a temperature of 60°C. EDX spectra and elemental mapping show signals of C, O, P, and F in Li metal due to electrolyte decomposition in the Li metal forming the solid electrolyte interface (SEI) layer. No vanadium (V) signal was present in the Li metal, suggesting that there was no dissolution of V in the cell during high temperature operation.

[0253] In this detailed description, reference is made to several embodiments and to the accompanying drawings which show, by way of illustration, certain exemplary embodiments of the technology. These embodiments are described in sufficient detail to enable those skilled in the art to practice the technology, it being understood that modifications to the various disclosed embodiments may be made by those skilled in the art.

[0254] Where the methods and steps described above indicate that certain events occur in a particular order, those skilled in the art will recognize that the order of certain steps may be altered and such alterations are subject to variations in the art. Additionally, certain steps may not only be performed sequentially, but also simultaneously in a parallel process where possible.

[0255] All publications, patents, and patent applications cited herein are incorporated by reference in their entirety as if each individual publication, patent, or patent application was specifically and individually indicated to be specifically and individually indicated herein. The disclosure of U.S. Patent Application Publication No. 2021 / 0184210A1, published June 17, 2021, is incorporated by reference herein.

[0256] The above-described embodiments, variations, and figures illustrate the utility and versatility of the present technology. Other embodiments that do not provide all of the features and advantages described herein may also be utilized without departing from the spirit and scope of the technology. Such modifications and variations are considered to be within the scope of the technology as defined by the following claims.

[0257] While various embodiments of the disclosed technology have been described above, it should be understood that they are presented by way of example only and not limitation. Similarly, various figures may depict example architectures or other configurations for the disclosed technology, which is done to aid in understanding the features and functionality that may be included in the disclosed technology. The disclosed technology is not limited to the example architectures or configurations shown, and the desired features can be implemented using various alternative architectures and configurations. It will be apparent to one skilled in the art how alternative functional, logical, or physical divisions and configurations can be implemented to implement the desired features of the technology disclosed herein. In addition, with respect to flow diagrams, operational descriptions, and methods, the order of steps shown herein does not mandate that the various embodiments be implemented to perform the described functions in the same order, unless the context dictates otherwise.

[0258] Although the disclosed technology has been described above with respect to various exemplary embodiments and implementations, it should be understood that various features, aspects, and functions described in one or more of the individual embodiments are not limited in their applicability to the particular embodiment for which they are described, but instead can be applied to one or more of the other embodiments of the disclosed technology, either alone or in various combinations, regardless of whether such features are presented as part of the described embodiment. Thus, the breadth and scope of the technology disclosed herein should not be limited by any of the exemplary embodiments described above. As will be apparent to one of ordinary skill in the art upon reading this patent application, the illustrated embodiments and various alternatives thereof can be practiced without being limited to the illustrated examples.

Claims

1. An anode material comprising a plurality of anode material particles, wherein the anode material particles include an inner phase containing lithium vanadium oxide and a surface coating disposed on the outer surface of the inner phase, and the lithium vanadium oxide is Li ａ V ｂ O ｃ (where a = 0.001 to 10, b = 1 to 3, c = 1 to 9, and a, b, and c are selected to maintain the charge balance of the Li ａ V ｂ O ｃ ) and has a composition given by, and the Li ａ V ｂ O ｃ can be reversibly lithiated, and the surface coating includes a species selected from the group consisting of carbon, metal oxides, metalloid oxides, metal fluorides, metalloid fluorides, metal phosphates, metalloid phosphates, and combinations thereof. An anode material comprising a plurality of anode material particles.

2. The anode material particles have an average effective diameter selected from about 0.01 micron to about 100 microns, the anode material according to Claim 1.

3. The surface coating is a non-porous coating without gaps, the anode material according to Claim 1.

4. The Li ａ V ｂ O ｃ is crystalline, the anode material according to claim 1.

5. The Li ａ V ｂ O ｃ at least 10% by weight of which is 【Number 1】 Having a disordered rock salt structure in the space group, the anode material according to any one of Claims 1 to 4.

6. The lithium vanadium oxide has a composition of Li ａ V ｂ O ｃ M ｄ (where d = 0.001 to 3, and a, b, c, and d are selected to maintain the charge balance of the Li ａ V ｂ O ｃ M ｄ ), and further contains a dopant M chemically or physically contained within the lithium vanadium oxide, and the Li ａ V ｂ O ｃ M ｄ can be reversibly lithiated, and 10% to 100% by weight of the Li ａ V ｂ O ｃ is 【Number 2】 Having a disordered rock salt structure in the space group, the anode material according to any one of Claims 1 to 4.

7. The anode material further includes one or more additional anode material components selected from the group consisting of silicon, silicon oxide, tin, tin oxide, phosphorus, carbonaceous species, and combinations thereof, and the carbonaceous species is different from the carbon (if any) included in the surface coating, the anode material according to Claim 1.

8. The Li ａ V ｂ O ｃ undergoes a volume change of about 0% to about 20% during one lithiumation - delithiation cycle, and the anode material according to claim 1, characterized in that the Li ａ V ｂ O ｃ undergoes a volume change of about 0% to about 20% during one lithiumation - delithiation cycle.

9. An anode including the anode material according to Claim 1.

10. The anode further includes one or more additional anode components selected from the group consisting of silicon, silicon oxide, tin, tin oxide, phosphorus, carbonaceous species, and combinations thereof, and the carbonaceous species is different from the carbon (if any) included in the surface coating, the anode according to Claim 9.

11. The anode further includes one or more binders, the anode according to Claim 9.

12. The anode has an anode volume porosity selected from about 5% to about 80%, the anode according to any one of Claims 9 to 11.

13. The anode has an average anode thickness of about 200 nanometers to about 500 microns, the anode according to any one of Claims 9 to 11.

14. The anode is present in a plurality of anode layers in the cell, and the cell further includes a plurality of cathode layers, a plurality of separator layers each disposed between an individual anode layer and a cathode layer, and a packet foil surrounding the plurality of anode layers, the plurality of separator layers, and the plurality of cathode layers, the anode according to any one of Claims 9 to 11.

15. The anode has a surface load of an anode material selected from about 0.2 mg / cm ２ to about 50 mg / cm ２ on at least one side of the anode, and the anode according to any one of claims 9 to 11.

16. The anode has an areal capacity of an anode material selected from about 0.05 mA·h / cm ２ to about 10 mA·h / cm ２ on at least one side of the anode, the anode according to any one of claims 9 to 11.

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