Solid-state lithium ion battery with long cycle life and ultrafast charge

Abstract

A solid state lithium ion battery with long cycle life and ultrafast charge is disclosed. Excellent cycle life can be achieved by means of an ultra-stable lithium vanadium oxide-based anode material-disordered rock salt Li < 3 > V < 2 > O < 5->. This anode material has an operating potential of about 0.6 V relative to Li / Li +, a 3D Li ion transport path, and a linear expansion rate of less than 2%. These characteristics enable rapid lithium transport, elimination of lithium metal precipitation, and provision of extremely long cycle life. In addition, due to no phase change or concentration polarization in the electrode, the use of a solid electrolyte such as Li5. 4PS4. 4Cl1.6 provides high rate performance and wide operating temperature. Solid state lithium ion batteries may be configured to provide a wide operating temperature range from-80 DEG C to 350 DEG C, maintaining 80% capacity in excess of 5,000 cycles, an ultrafast charge time of 3 minutes to 80% state of charge, an energy density in excess of 200 W * h / kg and 650 W * h / L.

Description

Priority data

[0001] This international patent application claims priority to U.S. Provisional Patent Application No. 63 / 524,256, filed June 30, 2023; U.S. Patent Application No. 18 / 756,013, filed June 27, 2024; and U.S. Patent Application No. 18 / 756,022, filed June 27, 2024, each of which is hereby incorporated herein by reference. field

[0002] This disclosure generally relates to solid-state lithium-ion batteries and methods for manufacturing and using solid-state lithium-ion batteries. background

[0003] Assuming 186 million (two-thirds) light-duty vehicles are converted from internal combustion engines to electric power, the electrification of transportation would require doubling the capacity of the U.S. power grid by 2050. This transition would require massive investments in new transmission lines and distribution systems, potentially exceeding $1 trillion by 2050, when all 186 million light-duty electric vehicles (EVs) will be in operation. The distribution system connecting to EV charging stations—the last mile of power delivery—including substations, circuits, switches, and transformers, will account for over 90% of this investment. Optimized EV charging and vehicle-to-grid integration could reduce the required distribution investment by approximately 70%, or $600 billion, by minimizing congestion at the distribution level, allowing bidirectional energy transfer, storing energy closer to loads, and integrating widely distributed renewable energy sources.

[0004] Rechargeable lithium-ion (Li-ion) batteries, capable of being safely charged and discharged at high rates, are desired for electrified transportation, portable electronic devices, grid storage, and other applications. Rechargeable Li-ion batteries have made mobile devices and personal computers essential to modern society. While significant advancements have been made in battery technology (e.g., energy density and structural stability), substantial progress is still needed in charging speed for Li-ion batteries. Li-ion batteries can potentially achieve high energy densities; however, the anode material limits the achievable charging rates.

[0005] Graphite has been the primary anode material for rechargeable lithium-ion batteries to date due to its low cost, high reversibility, and operating potential close to that of lithium metal. These properties have enabled batteries to achieve high specific energy and long cycle life. Currently, commercially available high-energy-density Li-ion batteries based on graphite anodes have achieved energy densities greater than 250 Wh / kg. However, these Li-ion batteries require several hours to charge. The demand for ultra-fast charging poses a significant challenge to graphite. At high charge rates, the anode potential in graphite can be driven below the lithium deposition potential, leading to lithium deposition and associated losses in lifespan and safety. For Li-ion batteries with graphite anodes, reducing the charging time to a few minutes sacrifices energy and severely reduces cycle life.

[0006] Slightly increasing the anode potential can overcome lithium deposition. Existing technology for ultrafast-charging Li-ion batteries uses commercially available anodes of lithium titanate (Li₄Ti₅O₂). 12 (LTO). Li4Ti5O 12 It is a generally safe material that can be charged in less than 10 minutes for many cycles, but its energy density is less than 90 W·h / kg. Li4Ti5O 12 Having relative to Li / Li + With a potential of approximately 1.5 V, when paired with a commercial 4 V cathode, a 2.5 V Li-ion battery is obtained. The low energy density primarily limits the application of LTOs to buses and multi-purpose vehicles.

[0007] Other embedded anodes such as LiV 0.5 Ti 0.5 The potential of S2 is approximately 1 V, still far above the desired potential. Alloy anodes (e.g., anodes using aluminum alloys) can achieve an ideal potential of 0.5 V and high capacity, but their cycle stability remains problematic even under normal operating conditions—not to mention for ultra-fast charging. Existing technology systems cannot simultaneously achieve a combination of high energy density and high power density, thus defining a technological gap.

[0008] A major challenge in the widespread adoption of vehicle-to-grid technology is battery degradation due to high wear and tear caused by the heavy use of batteries during frequent discharges (when driving EVs) and charging (when recharging when connected to the grid). Similar challenges exist for heavy-duty vehicles, construction vehicles, two-wheeled vehicles, boats, robots, drones, electric vertical takeoff and landing aircraft, and many other commercial applications.

[0009] Given the current technology, there is still a need for improved Li-ion batteries. In particular, there is a desire for safe Li-ion batteries that can be fast-charged in less than 10 minutes, have an energy density of at least 100 Wh / kg, and can operate for at least 1,000 cycles. Overview

[0010] This disclosure addresses the aforementioned needs in the art, as will now be outlined and then described in further detail below.

[0011] Some variations provide a solid-state lithium-ion battery that includes:

[0012] An anode layer comprising lithium vanadium oxide, wherein the lithium vanadium oxide has a composition of Li a V b O c The given composition, where a = 0.001–10, b = 1–3, c = 1–9, and a, b, and c are chosen to balance the charge of Li. a V b O c Li a V b O c It can be reversibly lithiumized, and in which Li a V b O c At least some of them are in The space group has a disordered rock salt structure;

[0013] A solid electrolyte layer comprising a solid electrolyte; and

[0014] The cathode layer contains cathode material.

[0015] The solid electrolyte layer is inserted between the anode layer and the cathode layer.

[0016] In some embodiments, approximately 0.01 wt% to 100 wt% of Li a V b O c exist The space group has a disordered rock salt structure.

[0017] In some embodiments, Li a V b O c Choose from the following groups: 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 0.001V2O3, LiV2O3, Li2V2O3, Li3V2O3, and combinations thereof.

[0018] In some embodiments, the lithium vanadium oxide further contains a dopant M chemically or physically contained within the lithium vanadium oxide, such that its composition consists of Li a V b O c M d Given, where d = 0.001-3, where a, b, c and d are chosen to balance Li. a V b O c M d Li a V b O c M d It can be reversibly lithiumized, and in which Li a V b O c M d At least some of them are in The space group exhibits a disordered rock salt structure. Approximately 0.01 wt% to 100 wt% Li a V b O c M d It is possible The space group has a disordered rock salt structure. The dopant M can be selected from the following groups: Na, K, Be, Mg, Ca, Zn, Fe, Co, Ni, Cu, Ag, Sc, B, Y, Al, La, Si, Ge, Sn, Ti, Zr, Mn, P, Nb, Ta, Cr, Mo, W, Se, N, S, F, Cl, Br, I, and combinations thereof.

[0019] In various embodiments, the solid electrolyte is selected from the group consisting of: oxides, sulfides, phosphates, argentite, β-alumina, LISICON, garnet, NASICON, perovskite, anti-perovskite, lithium nitride, lithium hydride, lithium phosphidotrielate and lithium phosphidotetrelate, lithium metal halides (e.g., lithium metal chloride), LIPON, lithium thiophosphate, and combinations thereof.

[0020] In some embodiments, the solid electrolyte is a sulfur-based superionic conductor, such as a halogen-containing lithium-silver-germanium ore. The halogen-containing lithium-silver-germanium ore can be selected from Li... 6-ε PS 5-ε X 1+εWhere -1 < ε ≤ 1, and where X = F, Cl, Br, I, or a combination thereof. For example, X can be Cl, and 0 ≤ ε ≤ 0.8. In some embodiments, the sulfur-based superionic conductor is selected from the group consisting of: Li₂S-P₂S₅, Li₇P₃S 11 Li 10 GeP2S 12 Li7SiPS8, Li3PS4, Li 1+2x Zn 1-x PS4 (0 ≤ x < 1) and its combinations.

[0021] In some embodiments, the solid electrolyte is an oxide-based superionic conductor. The oxide-based superionic conductor can be selected from the group consisting of: Li-Al₂O₃, Li₇La₃Zr₂O. 12 Li 2+2x Zn 1-x GeO4 (0 ≤ x ≤ 1), Li 1+ x Zr2Si x P 3-x O 12 (0 < x < 3)

[0022] La 2 / 3-x Li 3x TiO3 (0 < x < 2 / 3), Li x X 1 3X 2 2O 12 (X) 1 = La, Nd, Mg, or Ba; 2 = Te, Ta, Nb, Zr, or In; and 0 < x < 7), and their combinations.

[0023] In some embodiments, the solid electrolyte is a phosphate-based superionic conductor. The phosphate-based superionic conductor can be selected from the group consisting of: Li3PO4, Li... 1+x X 1 x X 2 2-x (PO4)3(X) 1 = Al, La, In, or Cr; X 2 = Ti, Ge, Zr, Hf, or Sn; and 0 < x < 2), and combinations thereof.

[0024] In some embodiments, the solid electrolyte is a nitride-based superionic conductor. The nitride-based superionic conductor can be selected from the group consisting of: Li3N, Li...x PO y N z (0 < x ≤ 3; 0 < y ≤ 4; and 0 < z ≤ 1), and their combinations.

[0025] In some embodiments, the solid electrolyte is a hydride-based superionic conductor. The hydride-based superionic conductor can be selected from the group consisting of: LiBH4, LiCB9H. 10 LiCB 11 H 12 , and their combinations.

[0026] In some embodiments, the solid electrolyte is selected from anti-perovskite, which is selected from the group consisting of Li3OCl, Li3OBr, Li3OF, Li3OI, and combinations thereof.

[0027] Cathode materials can be selected from, for example, the group consisting of: LiCoO2, LiMn2O4, Li2MnO3, LiFePO4, and LiNi. x Co y Al z O2 (x + y + z = 1), LiMn x Ni y O4 (x + y = 2), LiNi x Co y Mn z O2 (x + y + z = 1), LiFe x Mn y PO4 (x + y = 1), aLiNi x Co y Mn z O2∙(1-a)Li2MnO3 (0 < a < 1 and x + y + z = 1), and its combinations.

[0028] In some embodiments, the cathode material is LiNi x Co y Mn z O2. LiNi x Co y Mn z O2 can be, for example, LiNi 0.8 Co 0.1 Mn 0.1 O2.

[0029] In some solid-state lithium-ion batteries, the solid electrolyte is also contained within the anode layer. In these or other embodiments, the solid electrolyte is also contained within the cathode layer.

[0030] In some embodiments, the anode layer, cathode layer, or solid electrolyte layer further contains a noble metal in neutral or ionic form. The noble metal is typically present only in trace concentrations. The noble metal may be selected from the group consisting of: Au, Ag, Pt, Rh, Pd, Ru, Os, Ir, and combinations thereof.

[0031] The anode layer may further contain a second anode material selected from the group consisting of: silicon, silicon oxide, graphite, hard carbon, soft carbon, silicon-carbon composites, aluminum, magnesium, zinc, tin, tin oxide, and combinations thereof.

[0032] When the anode layer contains carbon as an additive, the anode carbon additive can be in sp form, sp... 2 Form and / or sp 3 Form. Anode carbon additives can be, for example, graphite, graphene, carbon nanotubes, carbon fibers, ultrafine carbon, activated carbon, carbon black, nanodiamonds, hard carbon, soft carbon, or combinations thereof.

[0033] The cathode layer may further contain sp in the form of sp 2 Form and / or sp 3 Cathode carbon additives can be in the form of graphite, graphene, carbon nanotubes, carbon fibers, ultrafine carbon, activated carbon, carbon black, nanodiamonds, hard carbon, soft carbon, or combinations thereof. Cathode carbon additives can be the same type of carbon as anode carbon additives, or they can be different types of carbon.

[0034] Typically, the cathode layer is disposed on a cathode current collector (e.g., an Al foil), and the anode layer is disposed on an anode current collector (e.g., a Cu foil).

[0035] In some embodiments, a solid-state lithium-ion battery includes multiple anode layers, multiple solid electrolyte layers, and multiple cathode layers.

[0036] In some embodiments, the solid-state lithium-ion battery is able to retain at least 80% of its capacity after 1,000, 5,000, 10,000, 15,000, or 20,000 cycles.

[0037] In some embodiments, solid-state lithium-ion batteries can be charged to 100% state of charge in 3 minutes or less.

[0038] In some embodiments, the solid-state lithium-ion battery has an energy density of at least 200 W·h / kg.

[0039] In some embodiments, the solid-state lithium-ion battery has an energy density of at least 650 W·h / L.

[0040] In some embodiments, solid-state lithium-ion batteries are capable of operating in a temperature range of approximately -80°C to approximately 350°C.

[0041] In some embodiments, solid-state lithium-ion batteries do not experience lithium metal deposition during operation.

[0042] In some embodiments, solid-state lithium-ion batteries are contained within a battery module / pack comprising multiple batteries. The battery module / pack may be contained within an electric vehicle. The electric vehicle may be, for example, an electric car, an electric truck, an electric bus, an electric motorcycle, or an electric aircraft.

[0043] In some embodiments, a solid-state lithium-ion battery is included within a portable device.

[0044] In some embodiments, a solid-state lithium-ion battery is included within a smart device.

[0045] In some embodiments, solid-state lithium-ion batteries are included within an emergency power backup system.

[0046] In some embodiments, solid-state lithium-ion batteries are included within a solar power storage system.

[0047] Another variation of the present invention provides a method for manufacturing a battery cell, the method comprising:

[0048] (a) Casting an anode material, an anode carbon additive, and a solid electrolyte onto a first substrate to form an anode, wherein the anode material comprises a plurality of anode material particles, wherein the anode material particles contain Li x V y O z The inner phase, where x = 0-10, y = 1-3, z = 1-9, and x, y, and z are chosen to balance the charge of Li. x V y O z ;

[0049] (b) Press the Li foil onto the anode to form a compacted anode;

[0050] (c) Casting cathode material, cathode carbon additive and solid electrolyte onto a second substrate to form a cathode;

[0051] (d) Stacking a solid electrolyte layer onto a compacted anode, wherein the solid electrolyte layer contains a solid electrolyte;

[0052] (e) Stacking the cathode onto a solid electrolyte layer;

[0053] (f) Surrounding multiple anode layers, multiple solid electrolyte layers, and multiple cathode layers with foil to form a battery cell; and

[0054] (g) Converting the compacted anode into a lithiation anode, the lithiation anode containing Li a V b O c Where a = 0.001-10, b = 1-3, c = 1-9, and a, b, and c are chosen to balance Li. a V b O c Li a V b O c It can be reversibly lithiumized, and in which Li a V b O c At least some of them are in The space group has a disordered rock salt structure.

[0055] As long as Li a V b O c Since the charge is balanced, non-integer values ​​of a, b, and c are all possible. In Li... a V b O c In some embodiments, a = 0.001-10. In Li a V b O c In various embodiments, '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, 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, including any intermediate range.

[0056] In Li a V b O c In some embodiments, b = 1.5-3.0. In Li a V b O cIn 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 intermediate range.

[0057] In Li a V b O c In some embodiments, c = 3-9. In Li 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 intermediate range.

[0058] In some methods, the anode material particles further contain a dopant M chemically or physically contained within the anode material particles to have the properties of Li a V b O c M d The given composition, where d = 0.001-3, is used where a, b, c, and d are chosen to balance the charge of Li. a V b O c M d Li a V b O c M d It can be reversibly lithiumized, and in which Li a V b O c M d At least some of them are in The space group has a disordered rock salt structure.

[0059] In some methods, an anode material, an anode carbon additive, and a solid electrolyte are coated on both sides of a layer of a first substrate; and a cathode material, a cathode carbon additive, and a solid electrolyte are coated on both sides of a layer of a second substrate.

[0060] In some methods, step (a) utilizes a casting pressure selected from about 10 kPa to about 250 MPa.

[0061] In some methods, step (b) utilizes a compaction pressure selected from about 10 kPa to about 100 MPa.

[0062] In some methods, the first substrate is a copper foil having a thickness of about 1 micrometer to about 100 micrometers.

[0063] In some methods, the second substrate is an aluminum foil having a thickness of about 1 micrometer to about 100 micrometers.

[0064] In some methods, the anode has an anode material loading selected from about 20 wt% to about 100 wt%.

[0065] In some methods, the anode has a concentration of about 0.2 mg / cm³ on at least one side of the anode. 2 Approximately 50 mg / cm 2 Anode material surface load.

[0066] In some methods, the anode has a polarity selected from about 0.05 mA·h / cm on at least one side of the anode. 2 Approximately 10 mA·h / cm 2 The areal capacity of the anode material.

[0067] Another variation provides a method for manufacturing a battery cell, the method comprising:

[0068] (a) Casting an anode material, an anode carbon additive, and a solid electrolyte onto a first substrate to form an anode, wherein the anode material comprises a plurality of anode material particles, wherein the anode material particles contain Li a V b O c The inner phase, where a = 0.001-10, b = 1-3, c = 1-9, and a, b, and c are chosen to balance Li. a V b O c ;

[0069] (b) Casting cathode material, cathode carbon additive and solid electrolyte onto a second substrate to form a cathode;

[0070] (c) Stacking a solid electrolyte layer onto the anode, wherein the solid electrolyte layer contains a solid electrolyte;

[0071] (d) Stacking the cathode onto a solid electrolyte layer; and

[0072] (e) A battery cell is formed by surrounding multiple anode layers, multiple solid electrolyte layers, and multiple cathode layers with foil.

[0073] Li a V b Oc It can be reversibly lithiumized, and in which Li a V b O c At least some of them are in The space group has a disordered rock salt structure.

[0074] The anode material particles may further contain a dopant M, chemically or physically contained within the anode material particles, to have the properties of Li a V b O c M d The given composition, where d = 0.001-3, is used where a, b, c, and d are chosen to balance the charge of Li. a V b O c M d Li a V b O c M d It can be reversibly lithiumized, and in which Li a V b O c M d At least some of them are in The space group has a disordered rock salt structure.

[0075] The anode material, anode carbon additive, and solid electrolyte can be coated on both sides of the layer of the first substrate. Similarly, the cathode material, cathode carbon additive, and solid electrolyte can be coated on both sides of the layer of the second substrate.

[0076] Step (a) can utilize a casting pressure, for example, selected from about 10 kPa to about 250 MPa.

[0077] The first substrate may be a copper foil having a thickness of about 1 micrometer to about 100 micrometers. The second substrate may be an aluminum foil having a thickness of about 1 micrometer to about 100 micrometers.

[0078] The manufactured anode may have an anode material loading selected from about 20 wt% to about 100 wt%.

[0079] The manufactured anode may have a concentration selected from about 0.2 mg / cm² on at least one side of the anode. 2 Approximately 50 mg / cm 2 Anode material surface load.

[0080] The manufactured anode may have a concentration selected from about 0.05 mA·h / cm on at least one side of the anode. 2 Approximately 10 mA·h / cm 2 The areal capacity of the anode material.

[0081] Another variation of the present invention provides a method for manufacturing a battery cell, the method comprising:

[0082] (a) Casting an anode material, an anode carbon additive, a solid electrolyte, and Li metal onto a first substrate to form an anode, wherein the anode material comprises a plurality of anode material particles, wherein the anode material particles contain Li x V y O z The inner phase, where x = 0-10, y = 1-3, z = 1-9, and x, y, and z are chosen to balance the charge of Li. x V y O z ;

[0083] (b) Casting cathode material, cathode carbon additive and solid electrolyte onto a second substrate to form a cathode;

[0084] (c) Stacking a solid electrolyte layer onto the anode, wherein the solid electrolyte layer contains a solid electrolyte;

[0085] (d) Stacking the cathode onto a solid electrolyte layer;

[0086] (e) Surrounding multiple anode layers, multiple solid electrolyte layers, and multiple cathode layers with foil to form a battery cell; and

[0087] (f) Converting the anode into a lithium-ion anode containing Li a V b O c Where a = 0.001-10, b = 1-3, c = 1-9, and a, b, and c are chosen to balance Li. a V b O c Li a V b O c It can be reversibly lithiumized, and in which Li a V b O c At least some of them are in The space group has a disordered rock salt structure.

[0088] In some methods of using Li metal in step (a), the Li metal is selected from the group consisting of Li metal powder, Li metal ingot, Li metal foil, and combinations thereof.

[0089] In some methods using Li metal in step (a), the anode material particles further contain a dopant M chemically or physically contained within the anode material particles to have the properties of Li.a V b O c M d The given composition, where d = 0.001-3, is used where a, b, c, and d are chosen to balance the charge of Li. a V b O c M d Li a V b O c M d It can be reversibly lithiumized, and in which Li a V b O c M d At least some of them are in The space group has a disordered rock salt structure.

[0090] In some methods of using Li metal in step (a), the anode material, anode carbon additive, and solid electrolyte are coated on both sides of a layer of the first substrate.

[0091] In some methods of using Li metal in step (a), cathode material, cathode carbon additive and solid electrolyte are coated on both sides of a layer of the second substrate.

[0092] In some methods of using Li metal in step (a), the step utilizes a casting pressure selected from about 10 kPa to about 250 MPa.

[0093] In some methods of using Li metal in step (a), the first substrate is a copper foil having a thickness of about 1 micrometer to about 100 micrometers, and / or the second substrate is an aluminum foil having a thickness of about 1 micrometer to about 100 micrometers.

[0094] In some methods of using Li metal in step (a), the anode has an anode material loading selected from about 20 wt% to about 100 wt%.

[0095] In some methods using Li metal in step (a), the anode has a concentration of about 0.2 mg / cm³ on at least one side of the anode. 2 Approximately 50 mg / cm 2 Anode material surface load.

[0096] In some methods using Li metal in step (a), the anode has a temperature selected from about 0.05 mA·h / cm² on at least one side of the anode. 2 Approximately 10 mA·h / cm 2 The areal capacity of the anode material.

[0097] Another variation of the present invention provides a method for manufacturing a battery cell, the method comprising:

[0098] (a) Casting an anode material, an anode carbon additive, and a solid electrolyte onto a first substrate to form an anode, wherein the anode material comprises a plurality of anode material particles, wherein the anode material particles contain Li x V y O z The inner phase, where x = 0-10, y = 1-3, z = 1-9, and x, y, and z are chosen to balance the charge of Li. x V y O z ;

[0099] (b) Casting cathode material, cathode carbon additive, solid electrolyte and lithium-containing compound onto a second substrate to form a cathode, wherein the lithium-containing compound is chemically different from the cathode material;

[0100] (c) Stacking the solid electrolyte layer onto the anode;

[0101] (d) Stacking the cathode onto a solid electrolyte layer;

[0102] (e) Surrounding multiple anode layers, multiple solid electrolyte layers, and multiple cathode layers with foil to form a battery cell; and

[0103] (f) Decomposing lithium-containing compounds to add lithium to anode material particles, thereby converting the anode into a lithiated anode containing Li. a V b O c Where a = 0.001-10, b = 1-3, c = 1-9, and a, b, and c are chosen to balance Li. a V b O c Li a V b O c It can be reversibly lithiumized, and in which Li a V b O c At least some of them are in The space group has a disordered rock salt structure.

[0104] In some methods using the decomposition of lithium-containing compounds in step (f), the anode material particles further contain a dopant M chemically or physically contained within the anode material particles to have a composition derived from Li a V b O c M dThe given composition, where d = 0.001-3, is used where a, b, c, and d are chosen to balance the charge of Li. a V b O c M d Li a V b O c M d It can be reversibly lithiumized, and in which Li a V b O c M d At least some of them are in The space group has a disordered rock salt structure.

[0105] In some methods of decomposing lithium-containing compounds in step (f), the lithium-containing compound is selected from the group consisting of lithium oxide, lithium hydride, lithium hydroxide, lithium hydroperoxide, lithium peroxide, lithium nitride, lithium carbonate, lithium bicarbonate, lithium sulfide, lithium sulfate, lithium squaric acid, lithium oxalate, lithium ketone malonate, lithium diketone succinate, and combinations thereof. In some embodiments, the lithium-containing compound is lithium oxide (Li₂O) and / or lithium nitride (Li₃N).

[0106] In some methods using the decomposition of lithium-containing compounds in step (f), the anode material, anode carbon additive, and solid electrolyte are coated on both sides of a layer of the first substrate. Similarly, the cathode material, cathode carbon additive, and solid electrolyte can be coated on both sides of a layer of the second substrate.

[0107] In some methods that use the decomposition of lithium-containing compounds in step (f), step (a) utilizes a casting pressure selected from about 10 kPa to about 250 MPa.

[0108] In some methods of decomposing lithium-containing compounds in step (f), the first substrate is a copper foil having a thickness of about 1 micrometer to about 100 micrometers.

[0109] In some methods of decomposing lithium-containing compounds in step (f), the second substrate is an aluminum foil having a thickness of about 1 micrometer to about 100 micrometers.

[0110] In some methods of using the decomposition of lithium-containing compounds in step (f), the anode has an anode material loading selected from about 20 wt% to about 100 wt%.

[0111] In some methods using the decomposition of lithium-containing compounds in step (f), the anode has a concentration of about 0.2 mg / cm³ on at least one side of the anode. 2 Approximately 50 mg / cm 2 Anode material surface load.

[0112] In some methods using the decomposition of lithium-containing compounds in step (f), the anode has a concentration selected from about 0.05 mA·h / cm² on at least one side of the anode. 2 Approximately 10 mA·h / cm 2 The areal capacity of the anode material.

[0113] In some methods that use the decomposition of lithium-containing compounds in step (f), this step is performed before the battery cell is charged. In other embodiments, step (f) is performed during the charging of the battery cell, such as when the battery cell is charged for the first time. In some embodiments, step (f) is performed both before and during the charging of the battery cell. Attached Figure Description

[0114] Figure 1 This is a schematic diagram of an exemplary solid-state lithium-ion battery.

[0115] Figure 2A and Figure 2B The performance of the all-solid-state Li||DRS-LVO battery cell using Li3PS4 solid electrolyte in Example 2 is shown.

[0116] Figure 2A The voltage characteristic curves of DRS-LVO at different rates at room temperature (approximately 25°C) are shown.

[0117] Figure 2B The voltage characteristic curves of DRS-LVO at different rates at 60°C are shown.

[0118] Figure 3A The voltage characteristic curves of DRS-LVO at different rates at 60°C are shown, demonstrating the all-solid-state Li using Li6PS5Cl solid electrolyte in Example 3. Performance of DRS-LVO battery cells.

[0119] Figure 3B The cycling performance of DRS-LVO at 1C is shown. Figure 3C The voltage characteristic curve of DRS-LVO at 1C during 200 cycles is shown in Example 3.

[0120] Figure 4A The voltage characteristic curves of DRS-LVO at different rates at 60°C are shown, demonstrating the all-solid-state Li using Li6PS5Cl solid electrolyte in Example 4. Performance of DRS-LVO battery cells.

[0121] Figure 4BThe cycling performance of DRS-LVO at 1C is shown in Example 4.

[0122] Figure 4C The voltage characteristic curve of DRS-LVO at 1C during 200 cycles is shown in Example 4.

[0123] Figure 5A The voltage characteristic curves of DRS-LVO at different rates at room temperature are shown, demonstrating the use of Cl-rich lithium-sulfur silver-germanium ore electrolyte Li in Example 5. 5.4 PS 4.4 Cl 1.6 All-solid-state Li Performance of DRS-LVO battery cells.

[0124] Figure 5B The cycling performance of DRS-LVO at 1C is shown in Example 5.

[0125] Figure 5C The voltage characteristic curve of DRS-LVO at 1C during 150 cycles is shown in Example 5.

[0126] Figure 6 The use of Cl-rich lithium-sulfur silver-germanium ore electrolyte Li was demonstrated. 5.4 PS 4.4 Cl 1.6 DRS-LVO The NMC811 solid-state full cell exhibits an average voltage of approximately 3.3 V when operating at a temperature of 60°C. Detailed Implementation

[0127] The principles, compositions, systems, and methods disclosed herein will be described in detail with reference to various non-limiting embodiments of the technology.

[0128] This specification will enable those skilled in the art to complete and use the present technology, and describes several embodiments, modifications, variations, alternatives, and uses of the present technology. These and other embodiments, features, and advantages of the present invention will become more apparent to those skilled in the art when taken in conjunction with the accompanying drawings and the following detailed description.

[0129] 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 they pertain.

[0130] Unless otherwise specified, all numerical values ​​representing conditions, concentrations, dimensions, etc., used in this specification and claims should be understood to be modified by the term "about" in all cases. Accordingly, unless otherwise specified, the numerical parameters set forth in the following specification and appended claims are approximations, which may vary at least depending on the specific analytical technique.

[0131] The term "comprising," synonymous with "including," "containing," or "characterized in," is inclusive or open-ended and does not exclude additional, unlisted elements or method steps. "Comprising" is a specialized term used in claims language, meaning that the specified claim element is essential, but other claim elements may be added and still constitute a concept within the scope of the claims.

[0132] As used herein, the phrase “consisting of” excludes any element, step, or component not specified in the claims. When the phrase “consisting of” (or variations thereof) appears in a clause of the body of a claim rather than immediately following the preamble, the phrase limits only the element set forth in that clause; other elements are not excluded from the claims as a whole. As used herein, the phrase “substantially constitutes” limits the scope of the claims to the specified elements or method steps, plus those that do not substantially affect the basis and one or more novel features of the claimed subject matter.

[0133] Regarding the terms “comprising” (synonymous with “including”), “consisting of”, and “substantially composed of”, when one of these three terms is used herein, the subject matter disclosed and claimed by this invention may include the use of any of the other two terms, except when used with Markush groups. Therefore, in some embodiments not explicitly enumerated, any instance of “comprising” may be replaced by “consisting of” or alternatively, “substantially composed of”. The term “comprising” should be interpreted as meaning “including, but not limited to”, etc.; the term “example” is used to provide exemplary instances of the items discussed, rather than an exhaustive or limiting list thereof.

[0134] Adjectives such as “conventional,” “traditional,” “normal,” “standard,” “known,” and similar terms should not be construed as limiting the described item to a given time period or to items available at a given time, but rather should be interpreted to encompass conventional, traditional, normal, or standard techniques that are available or known now or at any time in the future. Similarly, where this patent application relates to techniques that would be obvious or known to a person skilled in the art, such techniques encompass those that are obvious or known to a person skilled in the art now or at any time in the future.

[0135] In this specification, assumptions and theories are disclosed, and it should be understood that the invention is not limited to the assumptions and theories presented.

[0136] In this specification, unless otherwise specified, percentages of the concentration of components in the composition are all weight percentages (wt%).

[0137] As used in this specification and the appended claims, unless the context clearly indicates otherwise, the singular forms “a / an” and “the” include plural indicators. The term “a / an” should be interpreted as meaning “at least one,” “one or more,” etc. In some cases, the presence of expanded words and phrases such as “one or more,” “at least,” “but not limited to,” or other similar phrases should not be interpreted as indicating a desired or necessary narrower scope where such expanded phrases might not be present.

[0138] This invention provides a solid-state lithium-ion battery with a cycle life of >20,000 cycles and ultra-fast charging. The disclosed solid-state lithium-ion battery enables complete vehicle-to-grid (V2G) integration to reduce the cost of ownership of electric vehicles (EVs), ensure grid stability and the upcoming large-scale EV transition, and further increase the penetration of renewable energy into society. Excellent cycle life is achieved through an ultra-stable lithium vanadium oxide (LVO)-based anode material, preferably disordered rock salt lithium vanadium oxide (“DRS-LVO”), such as disordered rock salt Li3V2O5.

[0139] DRS-LVO anode material has relative Li / Li + It features an operating potential of approximately 0.6 V, a three-dimensional Li transport path, and a linear expansion rate of less than 2%. These characteristics make it virtually unaffected by lithium metal deposition, enabling rapid lithium transport and providing extremely long cycle life. Furthermore, in this disclosure, the use of a solid-state electrolyte (SE) allows for high rate performance and a wider operating temperature range due to the absence of concentration polarization in the electrodes and the absence of electrolyte phase transitions—such as freezing at low temperatures or vaporization of liquid electrolytes at high temperatures.

[0140] In some variants, DRS-LVO-based solid-state lithium-ion batteries exhibit excellent performance: (i) retaining 80% of capacity after >20,000 cycles; (ii) super-fast charging to 80% state of charge (SOC) in 3 minutes; (iii) energy density >200 W·h / kg and >650 W·h / L; and (iv) operating temperature range from about -80°C (193.15 K) to about 350°C (623.15 K), such as from about -60°C (213.15 K) to about 150°C (423.15 K) or from about -40°C (233.15 K) to about 120°C (393.15 K).

[0141] As mentioned in the background, a significant challenge to the widespread adoption of V2G is battery degradation due to increased wear and tear caused by increased use during driving and grid service. For existing Li-ion technologies, this degradation is largely determined by the graphite anode, especially at fast-charging rates. This invention is partly based on replacing graphite with DRS-LVO to effectively eliminate battery life limitations and enable widespread V2G adoption. Furthermore, the solid-state electrolyte significantly widens the battery operating temperature range to (i) increase battery pack energy density, (ii) improve rate performance to reduce charging time, and (iii) enhance safety by eliminating volatile liquids and gels. The disclosed battery can be used in a significant portion of the anticipated >11 TWh EV energy storage (186 million EVs, 60 kWh per EV), with full V2G capabilities. V2G can constitute the world's largest virtual power plant, increasing grid resilience, driving transportation decarbonization, efficiently integrating renewable energy, and creating new revenue streams for EV owners, thereby accelerating the transition to fully electrified transportation.

[0142] In some variants, the novel DRS-LVO is paired with superionic conductors such as halide-rich lithium sulfide germanium ore and high-energy cathodes. Many specific compositions are disclosed herein.

[0143] In some embodiments, the present invention provides an ultra-long cycle life solid-state battery comprising a DRS-LVO-based anode, a halide-rich lithium sulfide-silver-germanium ore solid electrolyte, and a nickel-rich NMC (nickel-manganese-cobalt) cathode. The breakthrough in ultra-long cycle life solid-state batteries is made possible at least in part by using a novel DRS-LVO-based anode material, which has the advantages of… Disordered rock salt structure in a spatial group.

[0144] DRS-LVO anodes offer numerous advantages. Firstly, DRS-LVO exhibits advantages relative to Li / Li ratios. +It operates at an average potential of 0.6 V, which is faster than existing Li4Ti5O technology. 12 The LTO fast-charging anode has a low potential of almost 1 V, but significantly higher than the Li metal deposition region, allowing for ultra-fast charging performance without sacrificing safety. The elevated potential, higher than that of Li metal or Si anodes, results in excellent stability with a solid-state electrolyte. Secondly, DRS-LVO can reversibly accommodate two Li ions, resulting in a high specific capacity of 260 mA·h / g (over 50% compared to LTO anodes), making the energy density of the solid-state battery equivalent to current high-energy Li-ion chemistry. Thirdly, the low Li-ion diffusion barrier of DRS-LVO enables its excellent rate performance. At 20 A / g equivalent to a 20-second charge, DRS-LVO has a discharge capacity of 109 mA·h / g, or 41% of its full capacity. Fourthly, DRS-LVO exhibits a linear expansion rate of less than 2%, significantly lower than that of graphite anodes (10%–12% along the c-axis). The low linear expansion rate enables excellent material stability of 35,000 lithium insertion / removal cycles in liquid electrolyte-based batteries, and is ideal for solid-state batteries where volume change is even more critical than in batteries with liquid electrolytes.

[0145] To date, achieving ultra-fast charging with solid-state batteries has been counterintuitive, as it is well known that mass transfer rates are higher in liquid phases compared to solid phases. However, the inventors of this invention have used inventive skill to identify the rate-limiting steps during battery operation. Several technical advantages can be achieved by shifting from a liquid electrolyte to a solid electrolyte:

[0146] 1. In solid electrolytes, there may be little or no concentration polarization. Concentration polarization in an electrolyte refers to an additional voltage drop (or "internal resistance") across the electrolyte and its ion concentration gradient, which exists in addition to the ohmic voltage drop associated with the average conductivity.

[0147] 2. In solid-state batteries, there is no desolvation process because there is no electrolyte solvent.

[0148] 3. The Li ion concentration in solid electrolytes (e.g., 10 to 50 mol / L) is much higher than that in conventional liquid electrolytes (e.g., 1–3 mol / L), by an order of magnitude or more. Lithium ion depletion in the electrolyte at anode composites has been considered a key reason for the limited utilization of graphite anodes at high rates.

[0149] 4. Solid-state electrolytes exhibit higher ionic conductivity and a significantly higher Li transference number than liquid electrolytes. The SE conductivity changes with temperature according to the Arrhenius rate. This results in a significant improvement in the kinetics of solid-state batteries compared to liquid electrolyte batteries.

[0150] In some embodiments, Ni-rich NMC materials are selected as cathodes due to their high capacity and high rate performance. For example, NMC811 (LiNi) 0.8 Mn 0.1 Co 0.1 O2) shows > 203 mA·h / g at 0.1C between 3.0 V and 4.3 V. Furthermore, NMC811 has 1.7 × 10⁻⁶ ppm. -5 High electronic conductivity of S / cm, with 10 -8 Up to 10 -9 cm 2 The high Li diffusion rate of / s enables its high rate performance. The excellent cycling stability of NMC811 in solid-state batteries at very high rates is also demonstrated.

[0151] Some variations provide a solid-state lithium-ion battery that includes:

[0152] An anode layer comprising lithium vanadium oxide, wherein the lithium vanadium oxide has a composition of Li a V b O c The given composition, where a = 0.001–10, b = 1–3, c = 1–9, and a, b, and c are chosen to balance the charge of Li. a V b O c Li a V b O c It can be reversibly lithiumized, and in which Li a V b O c At least some of them are in The space group has a disordered rock salt structure;

[0153] A solid electrolyte layer comprising a solid electrolyte; and

[0154] The cathode layer contains cathode material.

[0155] The solid electrolyte layer is inserted between the anode layer and the cathode layer.

[0156] In some embodiments, approximately 0.01 wt% to 100 wt% of Li a V b Oc exist The space group exhibits a disordered rock salt structure. Preferably, it contains at least 10 wt% Li. a V b O c exist The space group exhibits a disordered rock salt structure. More preferably, at least 50 wt% Li a V b O c exist The space group exhibits a disordered rock salt structure. Even more preferably, it contains at least 90 wt% Li. a V b O c exist The space group exhibits a disordered rock salt structure. Most preferably, virtually all Li... a V b O c exist The space group exhibits a disordered rock salt structure. In various embodiments, at least 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, 99.5 wt%, or 99.9 wt% (such as 100 wt%) of Li are present. a V b O c exist The space group has a disordered rock salt structure.

[0157] The disordered rock salt structure is described by Liu et al., “A disordered rock salt anode for fast-charging lithium-ion batteries”, Nature, Vol. 585, pp. 63-67 (2020), which is hereby cited and incorporated herein by reference. The disordered rock salt crystal structure can be... Indexed in the space group, where the cubic lattice parameter a = 4.095 Å. Li a V b O cThe disordered rock salt crystal structure is a lattice containing lithium (Li) and transition metal (V) arranged in a disordered (rather than strictly periodic) manner on a cation lattice. Oxygen atoms are closely packed to form a face-centered cubic structure. Most of the lithium (Li) and transition metal (V) are located in octahedral positions formed by oxygen. Lithium (Li) can also be distributed in tetrahedral positions formed by oxygen.

[0158] Disordered rock salt crystal structures contrast with ordered rock salt crystal structures, such as those found in NaCl, where sodium and chloride ions form a regular, ordered structure. In disordered rock salt crystal structures, the precise positions of metal ions vary, but the overall crystal structure still exists. This specification hereby incorporates, by reference, International Tables for Crystallography, Volume A: Space-group symmetry, Second Online Edition, edited by Aroyo, 2016.

[0159] The disordered crystal structure of rock salt also contrasts with the disordered amorphous structure lacking a lattice. For example, when Li... a V b O c When nominally Li3V2O5, the amorphous structure means that Li, V, and O atoms are randomly placed within the material, randomly combined with each other, and do not form crystals. Crystalline solids have well-defined edges and faces, diffract X-rays, and tend to have sharp melting points. In contrast, amorphous solids have irregular or curved surfaces, cannot give high-resolution X-ray diffraction patterns, and melt over a wide temperature range. In this invention, Li... a V b O c Preferably, it is crystalline, or has a crystallinity of at least 80%, at least 85%, at least 90%, at least 95%, at least 99%, or 100%. Li has a crystallinity of at least 80%. a V b O c This is referred to in this paper as crystalline LVO or c-LVO. The crystallinity of LVO can be measured using X-ray diffraction.

[0160] Li without any lithium a V b O c The precursor—typically vanadium pentoxide, V₂O₅—can be crystalline or amorphous. In principle, the disordered rock salt structure persists until at least one lithium atom is embedded in V₂O₅ (i.e., in Li₂O₅). a V b O cIn lithiation, a > 0 is required for the rock salt structure to be maintained. During lithiation, the rock salt structure is preferably maintained as the a value increases, even up to very high a values, such as 4, 5, or even greater. For example, in a preferred embodiment, the disordered rock salt structure is maintained by converting Li3V2O5 to Li4V2O5 or Li5V2O5. During lithiation, after the initial formation of a disordered rock salt structure following the introduction of lithium atoms, Li3V2O5 with a disordered rock salt crystal structure... a V b O c The fraction may increase further. In other embodiments, Li having a disordered rock salt crystal structure a V b O c The fraction remains relatively constant with increasing degree of lithiation (a value). In some embodiments, during the first discharge, Li a V b O c It can exhibit a superstructure of rock salt lattice, which disappears upon further cycling. The disappearance of the superstructure does not affect the disordered rock salt structure and electrochemical performance.

[0161] Li a V b O c It can exist in a non-lithiationd state, where Li a V b O c In this context, a = 0. During the use of the anode material, and possibly before the use of the anode material, Li... a V b O c It exists in a lithiated state, in which Li a V b O c In this case, a > 0.

[0162] In some embodiments, Li a V b O c Choose from the following groups: 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.

[0163] Lia V b O c It can have approximately 1.5 g / cm³ 3 Approximately 5.5 g / cm 3 The density. In various embodiments, Li a V b O c It has 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 / cm³ 3 The density, including any intermediate range.

[0164] The anode material may have an anode material volume porosity selected, for example, from about 5% to about 80%. In various embodiments, the anode material has an anode material volume porosity of about, at least about, or at most about 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, or 80%, including any intermediate range.

[0165] In some embodiments, the lithium vanadium oxide further contains a dopant M chemically or physically contained within the lithium vanadium oxide, such that its composition consists of Li a V b O c M d Given, where a = 0.001-10, b = 1-3, c = 1-9, and d = 0.001-3, where a, b, c, and d are chosen to balance Li. a V b O c M d And among them Li a V b O c M d It can be reversibly lithiumized. Formula Li a V b O c M d It is stoichiometric and does not necessarily mean that the dopant M is chemically bonded to any other substance present.

[0166] Dopant M can be selected from, for example, the group consisting of: Na, K, Be, Mg, Ca, Zn, Fe, Co, Ni, Cu, Ag, Sc, B, Y, Al, La, Si, Ge, Sn, Ti, Zr, Mn, P, Nb, Ta, Cr, Mo, W, Se, N, S, F, Cl, Br, I, and combinations thereof. Dopant may include one or more monovalent, divalent, trivalent, tetravalent, pentavalent, or hexavalent dopants. Li a V b O c M d There may be multiple dopants in the formula, in which case each dopant in the empirical formula may have d = 0.1-3.

[0167] Dopants can be used to modify the properties of lithium vanadium oxide. For example, dopants can be used to modulate lithiation, delithiation, or other kinetics; lithiation capacity; anode stability; lithiation-delithiation potential; electronic conductivity of the anode material; diffusion of lithium ions in the crystal structure of the anode material; thermal properties; density; and / or other factors.

[0168] The doped composition can have a disordered rock salt structure. The disordered rock salt lattice may or may not contain dopant elements. That is, in the presence of dopant M, in some embodiments, Li... a V b O c M d The disordered rock salt crystal structure is a lattice containing a disordered arrangement of Li, V, and M atoms at cation lattice sites. Alternatively or additionally, the dopant M may be located at different positions within the cation lattice of the disordered rock salt crystal structure, such as being randomly placed, or located in a different lattice that dominates the relationship between M and other atoms, possibly superimposed on the disordered rock salt crystal structure. In some embodiments, the presence of dopant M reduces the optimal amount of vanadium (b-value) in the disordered rock salt anode material. In some embodiments, the presence of dopant M reduces the optimal amount of lithium (a-value) in the disordered rock salt anode material. In other embodiments, the presence of a nonmetallic dopant M (e.g., M = N, S, F, Cl, Br, or I) reduces the optimal amount of oxygen (c-value) in the disordered rock salt anode material.

[0169] In a preferred embodiment using a dopant, Li a V b O c M d At least some of them are in The space group exhibits a disordered rock salt structure. Approximately 0.01 wt% to 100 wt% Li a V b O c M d It is possible The space group has a disordered rock salt structure.

[0170] Li a V b O c M d (Doped anode material) can have approximately 1.5 g / cm³. 3 Approximately 5.5 g / cm 3 The density. Preferably, at least 50 wt% or at least 90 wt% Li a V b O c M d exist The space group exhibits a disordered rock salt structure. In various embodiments, at least 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, 95 wt%, or 99 wt% (such as 100 wt%) of Li are present. a V b O c M d exist The space group has a disordered rock salt structure.

[0171] In some embodiments, the anode material particles have a shape selected from the group consisting of spheres, cylinders, cubes, irregular shapes, and combinations thereof. The anode material particles may have an average effective diameter, for example, selected from about 0.01 micrometers to about 100 micrometers. In various embodiments, the average effective diameter of the anode material particles is about, at least about, or at most about 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 micrometers, including any intermediate range. The anode material particles may have a unimodal or multimodal size distribution.

[0172] Particle size can be measured using 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 the size and size distribution of particles, typically in the submicron region (and even as low as 1 nanometer with the latest technology). Laser diffraction is a widely used technique for particle size measurement of materials ranging 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 can be performed directly on photomicrographs, scanning electron micrographs, or other images to estimate particle size and distribution.

[0173] In addition to lithium vanadium oxide, the anode layer may further contain a second anode material selected from the group consisting of: silicon, silicon oxide, carbon (in one or more forms, typically graphite, hard carbon, and / or soft carbon), silicon-carbon composites, aluminum, magnesium, zinc, tin, tin oxide, and combinations thereof. The second anode material may be physically mixed (e.g., blended) with lithium vanadium oxide and coated onto the lithium vanadium oxide, or a combination thereof.

[0174] The anode layer preferably contains sp in the form of sp 2 Form and / or sp 3 Anode carbon additives can be in the form of graphite, graphene, carbon nanotubes, carbon fibers (e.g., vapor-grown carbon fibers), non-graphitized carbon, ultrafine carbon, activated carbon, carbon black, nanodiamonds, hard carbon, soft carbon, or combinations thereof.

[0175] In some embodiments, the anode material is characterized by being chemically stable in the presence of air. In this disclosure, chemical stability in the presence of air is determined by maintaining at atmospheric pressure (1 bar) and room temperature (25°C) for at least one day, preferably at least one week, and more preferably at least one month.

[0176] In some embodiments, the anode material is characterized by being chemically stable in the presence of water. In this disclosure, chemical stability in the presence of water is determined by 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.

[0177] In some embodiments, the anode further comprises one or more adhesives. The adhesives hold the active anode materials together and bring them into contact with the anode substrate (e.g., copper foil). The adhesives also help hold the conductive carbon additive in place against the active material.

[0178] The adhesive may be a water-based adhesive, such as those 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 adhesive may be a non-water-based adhesive, such as those selected from the group consisting of polyvinylidene fluoride, poly(vinylidene fluoride-co-hexafluoropropylene), polytetrafluoroethylene, and combinations thereof.

[0179] The concentration range of the binder can be, for example, from about 0 wt% to about 50 wt% of the anode. In various embodiments, the binder aggregate has a total concentration of about, at least about, or at most about 0 wt%, 0.25 wt%, 0.5 wt%, 1 wt%, 2 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, or 80 wt%, including any intermediate range.

[0180] In some embodiments, the anode has an anode volumetric porosity selected from about 5% to about 80%. In various embodiments, the anode has an anode volumetric porosity of about, at least about, or at most about 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, or 80%, including any intermediate range.

[0181] In some embodiments, the anode has an average anode thickness of about 100 nanometers to about 500 micrometers. 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 intermediate range.

[0182] The anode layer may contain silicon and lithium vanadium oxide (Li). a V b O c For example, the anode layer may have a composition as disclosed in WO 2022 / 178246 A1, published August 25, 2022, which is incorporated herein by reference. Some variations utilize an anode material comprising: (a) a porous anode phase comprising silicon, wherein the porous phase is characterized by a porous phase volume porosity selected from about 5% to about 80%; and (b) a first solid mediator layer disposed outwardly on the porous anode phase, wherein the first solid mediator layer contains a lithium vanadium oxide material, wherein the lithium vanadium oxide material has a porosity of about 2.0 g / cm³. 3 Approximately 5.5 g / cm 3 The density of lithium vanadium oxide materials, where lithium vanadium oxide materials have the properties of Li a V b O c The given composition, where a = 0-10, b = 1-3, c = 1-9, and a, b, and c are chosen to balance the charge of Li. a Vb O c And among them Li a V b O c It can be reversibly lithilated. In some embodiments, the anode material is a core-shell material, wherein a first solid mediator layer forms a shell encapsulating the porous anode phase. In some embodiments, the anode material is a sandwich material, wherein the first solid mediator layer is disposed outwardly on a first side of the porous anode phase, wherein a second solid mediator layer is disposed outwardly on a second side of the porous anode phase, and wherein the second solid mediator layer contains a lithium vanadium oxide material. Silicon may be present in the porous anode phase at a concentration of about 1 wt% to 100 wt% Si. Silicon may be amorphous silicon, polycrystalline silicon, or monocrystalline silicon. Silicon may have an average particle size, for example, from about 10 nanometers to about 100 micrometers. Silicon may exist as particles, the particle geometry of which is selected, for example, from the group consisting of: spheres, cylinders, cubes, tubes, wires, sheets, fibers, irregular shapes, and combinations thereof.

[0183] In some embodiments of solid-state lithium-ion batteries, the anode layer further comprises a second anode material selected from the group consisting of silicon, silicon oxide, graphite, hard carbon, soft carbon, silicon-carbon composites, aluminum, magnesium, zinc, tin, tin oxide, and combinations thereof.

[0184] An anode can exist within a battery cell. A "battery cell" is an electrochemical battery unit that can generate electrical energy from a chemical reaction or use electrical energy to induce a chemical reaction.

[0185] The battery cell may further include a cathode, an electrolyte layer, and a foil surrounding the anode, electrolyte layer, and cathode, wherein the electrolyte layer electrically separates the anode from the cathode. An anode composite material may be disposed on a first substrate (e.g., copper foil) to form the anode, and a cathode composite material may be disposed on a second substrate (e.g., aluminum foil) to form the cathode. In a layered battery cell configuration, multiple layers of anode, electrolyte layer, and cathode may be present. These layers are repeatedly stacked to form a multilayer stack in a battery cell configuration, thereby forming an anode, electrolyte layer, cathode, electrolyte layer, anode, electrolyte layer, cathode, electrolyte layer, etc., depending on the total number of layers.

[0186] The foil isolates the anode-electrolyte-cathode assembly from the external environment. The foil can be made of polymers such as polyamide, polyester-polyurethane, polypropylene, and / or metals such as aluminum. The thickness of the foil can range from about 20 µm to about 200 µm.

[0187] In some embodiments, the anode has an anode material loading selected from about 20 wt% to about 100 wt%, such as about 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, or 100 wt%, including any intermediate range.

[0188] In some embodiments, the anode material areal loading on at least one side of the anode is selected from about 0.2 mg / cm². 2 Approximately 50 mg / cm 2 Such as approximately 0.2, 0.5, 1, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 mg / cm² on at least one side of the anode (e.g., on both sides of the anode). 2 This includes any intermediate range.

[0189] In some embodiments, the areal mass of the anode material on at least one side of the anode is selected from about 0.05 mA·h / cm². 2 Approximately 10 mA·h / cm 2 Such as approximately 0.05, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mA·h / cm on at least one side of the anode (e.g., on both sides of the anode). 2 This includes any intermediate range.

[0190] In some embodiments, the anode has a capacity ranging from about 50 mA·h / g to about 2500 mA·h / g, such as about 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, or 2500 mA·h / g, including any intermediate range.

[0191] In some embodiments, the anode has a negative-to-positive ratio (N / P ratio) ranging from about 0.5 to about 2, such as about 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, or 2.0, including any intermediate range.

[0192] Copper foil or other metal foil can be used as a substrate on which the anode material is placed. 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 intermediate range. In some embodiments, the anode compaction density can range from about 0.3 g / cm³. 3 Approximately 5 g / cm 3 Within the range, such as approximately 0.3, 0.4, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5 g / cm³. 3 This includes any intermediate range.

[0193] When the anode material is disposed on the substrate, it is typically disposed on both sides of the substrate layer. This is called a double layer. Within a cell, the number of double layers can vary widely, such as from 1 to approximately 50, for example, approximately 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, or more.

[0194] Anode materials may enable Li-ion batteries to charge within minutes without complex nano-sizing processes. These materials enable fast-charging batteries without sacrificing energy density. In some embodiments, the anode material can exhibit a voltage plateau ranging from about 0 V to about 2 V. This voltage potential range ensures that the anode potential reaches a value that will not cause lithium deposition at high currents. When using common cathode materials, this voltage potential range also ensures that the average cell voltage does not drop to less than about 1.5 V.

[0195] Cathode materials can be selected from, for example, the group consisting of: LiCoO2, LiMn2O4, Li2MnO3, LiFePO4, and LiNi. x Co y Al z O2 (x + y + z = 1), LiMn x Ni y O4 (x + y = 2), LiNi x Co y Mn z O2 (x + y + z = 1), LiFe x Mn y PO4 (x + y = 1), aLiNi x Co y Mn z O2∙(1-a)Li2MnO3 (0 < a < 1 and x + y + z = 1), and combinations thereof. In some embodiments, the cathode material is LiNi. x Co yMn z O2. LiNi x Co y Mn z O2 can be, for example, LiNi 0.8 Co 0.1 Mn 0.1 O2. Other cathode materials can be used. Based on the composition of each electrode, the cathode can be paired with the anode.

[0196] The cathode layer preferably further contains sp in the form of sp 2 Form and / or sp 3 Cathode carbon additives can be in the form of graphite, graphene, carbon nanotubes, carbon fibers (e.g., vapor-grown carbon fibers), non-graphitized carbon, ultrafine carbon, activated carbon, carbon black, nanodiamonds, hard carbon, soft carbon, or combinations thereof. Cathode carbon additives can be the same type of carbon as anode carbon additives, or they can be different types of carbon.

[0197] In some embodiments, the cathode may have a capacity, for example, ranging from about 50 mA·h / g to about 400 mA·h / g. In some embodiments, the active cathode material loading may range from about 50 wt% to about 100 wt%. In some embodiments, the coating weight on each side of the cathode may range from about 0.5 mg / cm³. 2 Approximately 50 mg / cm 2 Within the range. In some embodiments, the areal capacity per side of the cathode can be from about 0.2 mA·h / cm². 2 Approximately 10 mA·h / cm 2 Within the range.

[0198] In some embodiments, the cathode compaction density can be from about 0.3 g / cm³. 3 Approximately 5 g / cm 3 The aluminum foil can be used as a substrate on which the cathode material is placed. In some embodiments, the thickness of the aluminum foil can range from about 1 µm to about 100 µm. The number of cathode double layers can range, for example, from 1 to about 50.

[0199] Solid electrolytes facilitate the movement of ions between the cathode and anode during charging and discharging. During charging, lithium ions are transported from the cathode to the anode; during discharging, lithium ions are transported from the anode to the cathode.

[0200] In various embodiments, the solid electrolyte is selected from the group consisting of oxides, sulfides, phosphates, argentite, β-alumina, LISICON, garnet, NASICON, perovskite, anti-perovskite, lithium nitrides (e.g., lithium metal nitrides), lithium hydrides (e.g., lithium metal hydrides), lithium group 13 phosphides, lithium group 14 phosphides, lithium halides (e.g., lithium chloride), lithium metal halides (e.g., lithium metal chlorides), LIPON, lithium thiophosphate, and combinations thereof. The lithium metal chloride Li-M-Cl can utilize a non-lithium metal M, such as, but not limited to, Y, Tb, Lu, Sc, Er, In, or Zr. An exemplary lithium metal chloride is Li2ZrCl6. Another exemplary lithium metal chloride is Li3YCl3. Typically, in some embodiments, the solid electrolyte can be selected from lithium metal halides Li-MX, where M = Y, Tb, Lu, Sc, Er, In, or Zr; and X = Cl, Br, I. In this specification, "lithium metal halide" refers to a material that contains metals other than lithium.

[0201] In some embodiments, the solid electrolyte material may be based on oxides, sulfides, or phosphates, and may have a variety of crystal structures. Some examples of these structures include LISICON (lithium superion conductor) (e.g., Li...). 2+2x Zn 1- x GeO4, Li 14 Zn(GeO4)4, Li (3+x) Ge x V (1-x) O4, Li 3.5 Ge 0.5 V 0.5 O4, Li 3.6 Ge 0.6 V 0.4 O4, Li (4-x) Si (1-x) P x O4, Li 3.5 Si 0.5 P 0.5 O4, and / or Li 3.4 Si 0.4 P 0.6 O4); sulfide-silver-germanium mineral-like structure (e.g., Li6PS5X, X = Cl, Br, I); garnet (e.g., LLZO, Li7La3Zr2O) 12Examples of lithium electrolytes include: NASICON (sodium superionic conductor); lithium nitride (e.g., Li3N); lithium hydride (e.g., LiBH4); lithium group 13 or group 14 phosphides; perovskites (e.g., lithium lanthanum titanate, LLTO); and lithium metal halides (e.g., Li3YCl6 or Li3YBr6). Additionally, some inorganic solid electrolytes can be amorphous, resembling glass ceramics. Examples include lithium phosphoxynitride (LIPON) and lithium thiophosphate (Li2S-P2S5).

[0202] In some embodiments, the solid electrolyte is a sulfur-based superionic conductor, such as a halogen-containing lithium-silver-germanium ore. The halogen-containing lithium-silver-germanium ore can be selected from Li... 6-ε PS 5-ε X 1+ε Where -1 < ε ≤ 1, and where X = F, Cl, Br, I, or a combination thereof. For example, X can be Cl, and 0 ≤ ε ≤ 0.8. In some embodiments, the sulfur-based superionic conductor is selected from the group consisting of: Li₂S-P₂S₅, Li₇P₃S 11 Li 10 GeP2S 12 Li7SiPS8, Li3PS4, Li 1+2x Zn 1-x PS4 (0 ≤ x < 1) and its combinations.

[0203] In some embodiments, the solid electrolyte is an oxide-based superionic conductor. The oxide-based superionic conductor can be selected from the group consisting of: Li-Al₂O₃, Li₇La₃Zr₂O. 12 Li 2+2x Zn 1-x GeO4 (0 ≤ x ≤ 1), Li 1+ x Zr2Si x P 3-x O 12 (0 < x < 3)

[0204] La 2 / 3-x Li 3x TiO3 (0 < x < 2 / 3), Li x X 1 3X 2 2O 12 (X) 1 = La, Nd, Mg, or Ba; 2 = Te, Ta, Nb, Zr, or In; and 0 < x < 7), and their combinations.

[0205] In some embodiments, the solid electrolyte is a phosphate-based superionic conductor. The phosphate-based superionic conductor can be selected from the group consisting of: Li3PO4, Li... 1+x X 1 x X 2 2-x (PO4)3(X) 1 = Al, La, In, or Cr; X 2 = Ti, Ge, Zr, Hf, or Sn; and 0 < x < 2), and combinations thereof.

[0206] In some embodiments, the solid electrolyte is a nitride-based superionic conductor. The nitride-based superionic conductor can be selected from the group consisting of: Li3N, Li... x PO y N z (0 < x ≤ 3; 0 < y ≤ 4; and 0 < z ≤ 1), and their combinations.

[0207] In some embodiments, the solid electrolyte is a hydride-based superionic conductor. The hydride-based superionic conductor can be selected from the group consisting of: LiBH4, LiCB9H. 10 LiCB 11 H 12 , and their combinations.

[0208] In some embodiments, the solid electrolyte is selected from anti-perovskite, which is selected from the group consisting of Li3OCl, Li3OBr, Li3OF, Li3OI, and combinations thereof.

[0209] In some embodiments, the solid electrolyte layer contains a mixed electrolyte, i.e., a mixture of two or more different types of solid electrolytes. In some embodiments, the solid electrolyte layer contains several different layers of different solid electrolyte materials or is composed of such layers.

[0210] In some solid-state lithium-ion batteries, the solid electrolyte is also contained within the anode layer, such as... Figure 1 As depicted in [the text]. In these or other embodiments, the solid electrolyte is also contained within the cathode layer, as described in [the text]. Figure 1 As depicted in the text. The anode and cathode layers can be combined with different solid electrolytes.

[0211] In some embodiments, the anode layer, cathode layer, or solid electrolyte layer further contains a noble metal in neutral or ionic form. The noble metal is typically present only in trace concentrations. The noble metal may be selected from the group consisting of: Au, Ag, Pt, Rh, Pd, Ru, Os, Ir, and combinations thereof.

[0212] Typically, the cathode layer is disposed on a cathode current collector (e.g., an Al foil), and the anode layer is disposed on an anode current collector (e.g., a Cu foil).

[0213] In some embodiments, a solid-state lithium-ion battery includes multiple anode layers, multiple solid electrolyte layers, and multiple cathode layers.

[0214] Figure 1 This is a schematic diagram of an exemplary solid-state lithium-ion battery. Figure 1 In this configuration, a solid electrolyte is stacked between the DRS-LVO anode and cathode. The anode contains DRS-LVO anode material (depicted as gray spheres), conductive carbon (depicted as black curves), and solid electrolyte (depicted as yellow spheres). The cathode contains cathode material (depicted as light red spheres), conductive carbon (depicted as black curves), and solid electrolyte (depicted as yellow spheres). A layer of solid electrolyte (depicted as yellow spheres) without cathode or anode material or conductive carbon is present. Other materials, such as binders (not shown), may be present. Figure 1 In a typical battery cell, a single-layer cell consists of a copper (Cu) current collector, an anode layer, a solid electrolyte layer, a cathode layer, and an aluminum (Al) current collector stacked together. A typical battery cell is a multilayer cell formed by repeatedly stacking single-layer cells to create many stacked layers.

[0215] In some embodiments, the solid-state lithium-ion battery is capable of retaining at least 80% of its capacity after 5,000, 10,000, 15,000, or 20,000 cycles. In various embodiments, the solid-state lithium-ion battery is capable of retaining at least 80%, at least 85%, at least 90%, or at least 95% of its capacity after 10,000 cycles.

[0216] In some embodiments, the solid-state lithium-ion battery can be charged to 80%, 90%, or 100% state of charge in 3 minutes or less. In various embodiments, the solid-state lithium-ion battery can be charged to 80% state of charge in 2 minutes or less, or in 1 minute or less. In various embodiments, the solid-state lithium-ion battery can be charged to 90% state of charge in 2 minutes or less, or in 1 minute or less. In various embodiments, the solid-state lithium-ion battery can be charged to 95% state of charge in 3 minutes or less, or in 2 minutes or less, or in 1 minute or less. In various embodiments, the solid-state lithium-ion battery can be charged to 99% state of charge in 3 minutes or less, or in 2 minutes or less, or in 1 minute or less. In some embodiments, the solid-state lithium-ion battery can be charged to 100% state of charge in 3 minutes or less, or in 2 minutes or less, or in 1 minute or less.

[0217] In some embodiments, the solid-state lithium-ion battery has an energy density of at least 200 Wh / kg. In some embodiments, the solid-state lithium-ion battery has an energy density of at least 650 Wh / L. In various embodiments, the solid-state lithium-ion battery has an energy density of about, or at least about 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, or 750 Wh / L, including any intermediate range.

[0218] In some embodiments, solid-state lithium-ion batteries are capable of operating in a temperature range of approximately -80°C to approximately 350°C.

[0219] In some embodiments, solid-state lithium-ion batteries do not experience lithium metal deposition during operation.

[0220] In some embodiments, solid-state lithium-ion batteries are contained within a battery module or battery pack that includes multiple batteries. A battery pack may contain multiple battery modules. Battery modules or packs may be included, for example, in electric vehicles or various other battery applications.

[0221] In some embodiments, solid-state lithium-ion batteries are used in electric vehicles. Electric vehicles can be, for example, electric cars, electric trucks, electric buses, electric locomotives, or electric aircraft. Major automotive companies are exploring solid-state batteries to extend driving range and reduce charging time. Buses and trucks requiring longer range and durability are also potential beneficiaries of the disclosed solid-state lithium-ion batteries. Heavy machinery utilizing solid-state lithium-ion batteries allows for more efficient and safer operation in mining and construction.

[0222] In some embodiments, solid-state lithium-ion batteries are used in marine applications. For example, electric or hybrid vessels using solid-state lithium-ion batteries can reduce emissions and fuel consumption during maritime transport.

[0223] In some embodiments, solid-state lithium-ion batteries are incorporated into portable devices such as laptops or smart devices. For example, in the smartphone sector, technology companies are researching solid-state batteries to improve safety and battery life. In the wearable technology sector (e.g., smartwatches and fitness trackers), there is a desire for more compact and longer-lasting batteries for these devices. In the smart home device sector, home energy storage systems can be integrated with home solar systems to provide reliable power during power outages or off-peak periods.

[0224] In some embodiments, solid-state lithium-ion batteries are included within an emergency power backup system. Emergency power backup systems can essentially be used in any application requiring reliable power, including homes, offices, warehouses, laboratories, hospitals, industrial plants (including but not limited to electrolysis facilities), data centers, satellites, electric vehicles, etc. Emergency power backup systems are also important for telecommunications infrastructure.

[0225] In some embodiments, solid-state lithium-ion batteries are used in portable power stations. Portable power stations are useful in remote locations where existing power infrastructure is not easily accessible. Portable power stations can also be used for emergency power supply, such as in events during natural disasters or war zones.

[0226] In some embodiments, solid-state lithium-ion batteries are included within the energy storage system. Grid energy storage systems may employ battery modules / packs comprising multiple disclosed solid-state lithium-ion batteries to better utilize and store solar and wind energy, thereby smoothing the variability of renewable energy sources.

[0227] In some embodiments, solid-state lithium-ion batteries are incorporated within, for example, solar power storage systems, wind power storage systems, or hydroelectric power storage systems. These embodiments are useful because renewable electricity supply is often mismatched with electricity demand, and sometimes there may be nowhere to consume the excess electricity generated. Solid-state lithium-ion battery systems can be configured to receive excess electricity and store it for later use when demand exceeds dynamic supply, thereby returning the electricity to the local grid.

[0228] In some embodiments, solid-state lithium-ion batteries are used in aerospace applications. For drones, solid-state batteries can help them fly for longer periods and carry more payload. For satellites, increased energy density can extend the operational lifespan of satellites and other spacecraft.

[0229] In some embodiments, solid-state lithium-ion batteries are used in military or defense applications. In the field of portable electronic devices for soldiers, there is significant interest in improving the reliability of devices used in field operations. For military vehicles, solid-state lithium-ion batteries can provide a more reliable and safer energy solution for vehicles operating in extreme environments.

[0230] In some embodiments, solid-state lithium-ion batteries are used in medical devices. For example, implantable medical devices such as pacemakers and neurostimulators benefit from the improved safety and lifespan of solid-state lithium-ion batteries. In the field of wearable robotics, such as exoskeletons used for medical rehabilitation, solid-state lithium-ion batteries can improve battery life and reduce weight to assist mobility.

[0231] Exemplary methods for preparing and using lithium vanadium oxide will now be further described.

[0232] Some variations of the present invention provide a method for manufacturing a battery cell, the method comprising:

[0233] (a) Casting an anode material, an anode carbon additive, and a solid electrolyte onto a first substrate to form an anode, wherein the anode material comprises a plurality of anode material particles, wherein the anode material particles contain Li x V y O z The inner phase, where x = 0-10, y = 1-3, z = 1-9, and x, y, and z are chosen to balance the charge of Li. x V y O z ;

[0234] (b) Press the Li foil onto the anode to form a compacted anode;

[0235] (c) Casting cathode material, cathode carbon additive and solid electrolyte onto a second substrate to form a cathode;

[0236] (d) Stacking a solid electrolyte layer onto a compacted anode, wherein the solid electrolyte layer contains a solid electrolyte;

[0237] (e) Stacking the cathode onto a solid electrolyte layer;

[0238] (f) Surrounding multiple anode layers, multiple solid electrolyte layers, and multiple cathode layers with foil to form a battery cell; and

[0239] (g) Converting the compacted anode into a lithiation anode, the lithiation anode containing Li a V b O c Where a = 0.001-10, b = 1-3, c = 1-9, and a, b, and c are chosen to balance Li. a V b O c Li a V b O c It can be reversibly lithiumized, and in which Li a V b O c At least some of them are in The space group has a disordered rock salt structure.

[0240] In some methods, the anode material particles further contain a dopant M chemically or physically contained within the anode material particles to have the properties of Li a V b O c M dThe given composition, where d = 0.001-3, is used where a, b, c, and d are chosen to balance the charge of Li. a V b O c M d Li a V b O c M d It can be reversibly lithiumized, and in which Li a V b O c M d At least some of them are in The space group has a disordered rock salt structure.

[0241] Disordered rock salt Li a V b O c Or Li a V b O c M d The raw materials can be vanadium oxides with different initial purities, such as V₂O₅ (vanadium pentoxide), such as low-grade materials, < 98 wt% V₂O₅; medium-grade materials, 98 wt%-99 wt% V₂O₅; or high-grade materials, > 99 wt% V₂O₅. V₂O₅ can be monocrystalline, polycrystalline, or amorphous. V₂O₅ can be in hydrated form. The particle size of V₂O₅ (or other vanadium oxides, such as VO, VO₂, or V₂O₃) can be, for example, from about 0.2 micrometers to about 100 micrometers, and can have a narrow, medium, or large particle size distribution or a multi-peak particle size distribution. Vanadium oxide particles can be spherical, columnar, cubic, flake-like, irregularly shaped, or a mixture of different shapes.

[0242] When using dopants, the dopants can be incorporated after lithiation, that is, the dopants are added to Li. a V b O c Li a V b O c M d Alternatively or additionally, the dopant can be incorporated into V₂O₅ prior to lithiation to form doped vanadium oxide V. b O c M d Where b = 1-3, c = 1-9, and d = 0.001-3. The doped vanadium oxide can be a low-grade material, <98 wt% V. b O c M d Medium-grade material, 98 wt%-99 wt% Vb O c M d Or high-grade materials, >99 wt% V b O c M d V b O c M d It can be monocrystalline, polycrystalline, or amorphous. V b O c M d The particle size can be, for example, from about 0.2 micrometers to about 100 micrometers, and can have a narrow, medium or large particle size distribution or a multi-peak particle size distribution. Doped vanadium oxide V b O c M d The particles can be spherical, cylindrical, cubic, flake-like, irregular in shape, or a mixture of different shapes.

[0243] In some methods, an anode material, an anode carbon additive, and a solid electrolyte are coated on both sides of a layer of a first substrate; and a cathode material, a cathode carbon additive, and a solid electrolyte are coated on both sides of a layer of a second substrate.

[0244] In some methods, step (a) utilizes a casting pressure selected from about 10 kPa to about 250 MPa. In various embodiments, the casting pressure is about, at least about, or at most about 0.1, 1, 10, or 100 MPa, including any intermediate range.

[0245] In some methods, step (b) utilizes a compaction pressure selected from about 1 MPa to about 100 MPa. In various embodiments, the compaction pressure is about, at least about, or at most about 1, 10, or 100 MPa, including any intermediate range.

[0246] In some methods, the first substrate is a copper foil having a thickness of about 1 micrometer to about 100 micrometers. In some methods, the second substrate is an aluminum foil having a thickness of about 1 micrometer to about 100 micrometers.

[0247] In some methods, the anode has an anode material loading selected from about 20 wt% to about 100 wt%. In some methods, the anode has a loading selected from about 0.2 mg / cm³ on at least one side of the anode. 2 Approximately 50 mg / cm 2 The areal loading of the anode material. In some methods, the anode has a material loading selected from about 0.05 mA·h / cm on at least one side of the anode. 2 Approximately 10 mA·h / cm 2 The areal capacity of the anode material.

[0248] Another variation provides a method for manufacturing a battery cell, the method comprising:

[0249] (a) Casting an anode material, an anode carbon additive, and a solid electrolyte onto a first substrate to form an anode, wherein the anode material comprises a plurality of anode material particles, wherein the anode material particles contain Li a V b O c The inner phase, where a = 0.001-10, b = 1-3, c = 1-9, and a, b, and c are chosen to balance Li. a V b O c ;

[0250] (b) Casting cathode material, cathode carbon additive and solid electrolyte onto a second substrate to form a cathode;

[0251] (c) Stacking a solid electrolyte layer onto the anode, wherein the solid electrolyte layer contains a solid electrolyte;

[0252] (d) Stacking the cathode onto a solid electrolyte layer; and

[0253] (e) A battery cell is formed by surrounding multiple anode layers, multiple solid electrolyte layers, and multiple cathode layers with foil.

[0254] Li a V b O c It can be reversibly lithiumized, and in which Li a V b O c At least some of them are in The space group has a disordered rock salt structure.

[0255] The anode material particles may further contain a dopant M, chemically or physically contained within the anode material particles, to have the properties of Li a V b O c M d The given composition, where d = 0.001-3, is used where a, b, c, and d are chosen to balance the charge of Li. a V b O c M d Li a V b O c M d It can be reversibly lithiumized, and in which Li a V b O c M d At least some of them are in The space group has a disordered rock salt structure.

[0256] The anode material, anode carbon additive, and solid electrolyte can be coated on both sides of the layer of the first substrate. Similarly, the cathode material, cathode carbon additive, and solid electrolyte can be coated on both sides of the layer of the second substrate.

[0257] Step (a) may utilize a casting pressure, for example, selected from about 10 kPa to about 250 MPa. In various embodiments, the casting pressure is about, at least about, or at most about 0.1, 1, 10, or 100 MPa, including any intermediate range.

[0258] The first substrate may be a copper foil having a thickness of about 1 micrometer to about 100 micrometers. The second substrate may be an aluminum foil having a thickness of about 1 micrometer to about 100 micrometers.

[0259] The manufactured anode (i.e., the anode produced in step (a)) may have an anode material loading selected from about 20 wt% to about 100 wt%. The manufactured anode may have a loading selected from about 0.2 mg / cm³ on at least one side of the anode. 2 Approximately 50 mg / cm 2 The anode material surface loading. The manufactured anode may have a content selected from about 0.05 mA·h / cm on at least one side of the anode. 2 Approximately 10 mA·h / cm 2 The areal capacity of the anode material.

[0260] Another variation of the present invention provides a method for manufacturing a battery cell, the method comprising:

[0261] (a) Casting an anode material, an anode carbon additive, a solid electrolyte, and Li metal onto a first substrate to form an anode, wherein the anode material comprises a plurality of anode material particles, wherein the anode material particles contain Li x V y O z The inner phase, where x = 0-10, y = 1-3, z = 1-9, and x, y, and z are chosen to balance the charge of Li. x V y O z ;

[0262] (b) Casting cathode material, cathode carbon additive and solid electrolyte onto a second substrate to form a cathode;

[0263] (c) Stacking a solid electrolyte layer onto the anode, wherein the solid electrolyte layer contains a solid electrolyte;

[0264] (d) Stacking the cathode onto a solid electrolyte layer;

[0265] (e) Surrounding multiple anode layers, multiple solid electrolyte layers, and multiple cathode layers with foil to form a battery cell; and

[0266] (f) Converting the anode into a lithium-ion anode containing Li a V b O c Where a = 0.001-10, b = 1-3, c = 1-9, and a, b, and c are chosen to balance Li. a V b O c Li a V b O c It can be reversibly lithiumized, and in which Li a V b O c At least some of them are in The space group has a disordered rock salt structure.

[0267] In some methods of using Li metal in step (a), the Li metal is selected from the group consisting of Li metal powder, Li metal ingot, Li metal foil, and combinations thereof.

[0268] In some methods using Li metal in step (a), the anode material particles further contain a dopant M chemically or physically contained within the anode material particles to have the properties of Li. a V b O c M d The given composition, where d = 0.001-3, is used where a, b, c, and d are chosen to balance the charge of Li. a V b O c M d Li a V b O c M d It can be reversibly lithiumized, and in which Li a V b O c M d At least some of them are in The space group has a disordered rock salt structure.

[0269] In some methods of using Li metal in step (a), the anode material, anode carbon additive, and solid electrolyte are coated on both sides of a layer of the first substrate.

[0270] In some methods of using Li metal in step (a), cathode material, cathode carbon additive and solid electrolyte are coated on both sides of a layer of the second substrate.

[0271] In some methods of using Li metal in step (a), this step utilizes a casting pressure selected from about 10 kPa to about 250 MPa. In various embodiments, the casting pressure is about, at least about, or at most about 0.1, 1, 10, or 100 MPa, including any intermediate range.

[0272] In some methods of using Li metal in step (a), the first substrate is a copper foil having a thickness of about 1 micrometer to about 100 micrometers, and / or the second substrate is an aluminum foil having a thickness of about 1 micrometer to about 100 micrometers.

[0273] In some methods using Li metal in step (a), the anode has an anode material loading selected from about 20 wt% to about 100 wt%. The anode may have a loading selected from about 0.2 mg / cm³ on at least one side. 2 Approximately 50 mg / cm 2 The anode material surface loading. The anode may have a content selected from about 0.05 mA·h / cm on at least one side of the anode. 2 Approximately 10 mA·h / cm 2 The areal capacity of the anode material.

[0274] Another variation of the present invention provides a method for manufacturing a battery cell, the method comprising:

[0275] (a) Casting an anode material, an anode carbon additive, and a solid electrolyte onto a first substrate to form an anode, wherein the anode material comprises a plurality of anode material particles, wherein the anode material particles contain Li x V y O z The inner phase, where x = 0-10, y = 1-3, z = 1-9, and x, y, and z are chosen to balance the charge of Li. x V y O z ;

[0276] (b) Casting cathode material, cathode carbon additive, solid electrolyte and lithium-containing compound onto a second substrate to form a cathode, wherein the lithium-containing compound is chemically different from the cathode material;

[0277] (c) Stacking the solid electrolyte layer onto the anode;

[0278] (d) Stacking the cathode onto a solid electrolyte layer;

[0279] (e) Surrounding multiple anode layers, multiple solid electrolyte layers, and multiple cathode layers with foil to form a battery cell; and

[0280] (f) Decomposing lithium-containing compounds to add lithium to anode material particles, thereby converting the anode into a lithiated anode containing Li. a V b O c Where a = 0.001-10, b = 1-3, c = 1-9, and a, b, and c are chosen to balance Li. a V b O c Li a V b O c It can be reversibly lithiumized, and in which Li a V b O c At least some of them are in The space group has a disordered rock salt structure.

[0281] In some methods using the decomposition of lithium-containing compounds in step (f), the anode material particles further contain a dopant M chemically or physically contained within the anode material particles to have a composition derived from Li a V b O c M d The given composition, where d = 0.001-3, is used where a, b, c, and d are chosen to balance the charge of Li. a V b O c M d Li a V b O c M d It can be reversibly lithiumized, and in which Li a V b O c M d At least some of them are in The space group has a disordered rock salt structure.

[0282] In some methods of decomposing lithium-containing compounds in step (f), the lithium-containing compound is selected from the group consisting of lithium oxide, lithium hydride, lithium hydroxide, lithium hydroperoxide, lithium peroxide, lithium nitride, lithium carbonate, lithium bicarbonate, lithium sulfide, lithium sulfate, lithium squaric acid, lithium oxalate, lithium ketone malonate, lithium diketone succinate, and combinations thereof. In some embodiments, the lithium-containing compound is lithium oxide (Li₂O) and / or lithium nitride (Li₃N). For example, when the lithium-containing compound is Li₂O, decomposition may cause reaction 2Li₂O 4 Li + O2, where Li atoms enter the anode material (forming Li a V b O c And oxygen escapes from the system as a gas.

[0283] In step (f), the degree of lithium atom transfer from the lithium-containing compound to the anode material can be from about 10% to 100%, preferably at least 50%, at least 75%, or at least 90%.

[0284] In some methods using the decomposition of lithium-containing compounds in step (f), the anode material, anode carbon additive, and solid electrolyte are coated on both sides of a layer of the first substrate. Similarly, the cathode material, cathode carbon additive, and solid electrolyte can be coated on both sides of a layer of the second substrate.

[0285] In some methods that use the decomposition of lithium-containing compounds in step (f), step (a) utilizes a casting pressure selected from about 10 kPa to about 250 MPa. In various embodiments, the casting pressure is about, at least about, or at most about 0.1, 1, 10, or 100 MPa, including any intermediate range.

[0286] In some methods using the decomposition of lithium-containing compounds in step (f), the first substrate is a copper foil having a thickness of about 1 micrometer to about 100 micrometers. In some methods, the second substrate is an aluminum foil having a thickness of about 1 micrometer to about 100 micrometers.

[0287] In some methods using the decomposition of lithium-containing compounds in step (f), the anode has an anode material loading selected from about 20 wt% to about 100 wt%. The anode may have a loading selected from about 0.2 mg / cm³ on at least one side. 2 Approximately 50 mg / cm 2 The anode material surface loading. The anode may have a content selected from about 0.05 mA·h / cm on at least one side of the anode. 2 Approximately 10 mA·h / cm 2 The areal capacity of the anode material.

[0288] In some methods that use the decomposition of lithium-containing compounds in step (f), this step is performed before the battery cell is charged. In other embodiments, step (f) is performed during the charging of the battery cell, such as when the battery cell is charged for the first time. In some embodiments, step (f) is performed both before and during the charging of the battery cell. This can be done, for example, when it is desired to decompose a certain amount of lithium-containing compound (e.g., Li3N) at high temperatures before the battery cell is charged.

[0289] Battery charging / discharging current can be expressed as the C-rate to normalize it relative to the battery capacity. The C-rate is a measure of the rate at which a battery charges / discharges relative to its maximum capacity. A 1C-rate means that the charging / discharging current will charge / discharge the battery in one hour. For a battery with a capacity of 10 A·h (ampere-hour), this is equivalent to a charging / discharging current of 10 A (amperes). A 20C-rate for such a battery would be 200 A, and a C / 2-rate would be 5 A.

[0290] In typical usage, the battery cell is repeatedly charged and discharged in multiple charge-discharge cycles, where Li a V b O c The battery cell is reversibly lithiated and delithiated multiple times. For example, the battery cell can be charged and discharged in 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.

[0291] When the battery cell undergoes at least one charge-discharge cycle, the lithium vanadium oxide material preferably has a volume change of 0% to about 10% during one or more charge-discharge cycles. In various embodiments, after one charge-discharge cycle, the lithium vanadium oxide material has a volume change of about, or at most about, 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 intermediate range. 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 lithium vanadium oxide material has a volume change of about, or at most about, 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 intermediate range.

[0292] In various embodiments, the battery system can be recharged in about, or less than about 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.2, or 0.1 minutes.

[0293] In some embodiments, the techniques disclosed in this invention can be used in battery systems that outperform conventional graphite battery packs and have a smaller number of battery cells. Such battery systems can utilize any (or more) of the disclosed anode and / or solid electrolyte materials and can be combined with 4 V high-capacity cathodes such as LiCoO2, Li-rich oxides, and / or Li(NiMnCo)O2 layered oxides. The battery systems are suitable for many commercial applications, including electric vehicles, smart devices, and high-power portable devices with high energy density.

[0294] Those skilled in the field of batteries will understand that the principles of battery design, including calculation, modeling, simulation, and engineering, can be implemented using this disclosure and the benefits of anode materials. Benefiting from this disclosure, those skilled in the field of batteries will understand how to scale up or down battery cells for different battery applications.

[0295] In some embodiments of the invention, one or more individual components of a solid-state lithium-ion battery are manufactured and then sent to another party for integration into a battery cell. In some embodiments of the invention, battery cells are manufactured and then sent to another party for integration into a final device or vehicle. In some embodiments of the invention, battery cells are manufactured and then sent to another party for integration into a module. In some embodiments of the invention, modules are manufactured and then sent to another party for integration into a final device or vehicle. In some embodiments of the invention, battery cells are manufactured and then sent to another party for integration into a battery pack. In some embodiments of the invention, modules are manufactured and then sent to another party for integration into a battery pack. In some embodiments of the invention, battery packs are manufactured and then sent to another party for integration into a final device or vehicle.

[0296] In this detailed description, reference has been made to various embodiments and accompanying drawings, wherein specific exemplary embodiments of the present technology are shown by way of illustration. These embodiments have been described in sufficient detail to enable those skilled in the art to practice the present technology, and it should be understood that modifications can be made by those skilled in the art to various disclosed embodiments.

[0297] When the above methods and steps specify that certain events occur in a certain order, those skilled in the art will recognize that the order of certain steps can be modified, and such modifications are made according to variations of this technology. Furthermore, some steps can be performed simultaneously as a parallel process where possible, or they can be performed sequentially.

[0298] All publications, patents, and patent applications cited in this specification are incorporated herein by reference in their entirety as if each publication, patent, or patent application had been expressly and individually set forth herein. This disclosure hereby incorporates, by reference only, U.S. Patent Application Publication No. 2021 / 0184210 A1, published June 17, 2021. This disclosure also hereby incorporates, by reference only, U.S. Patent Application Publication No. 20230120748 A1, published April 20, 2023.

[0299] The above embodiments, variations, and drawings are intended to indicate the practicality and versatility of the invention. Other embodiments not providing all the features and advantages set forth herein may be utilized without departing from the spirit and scope of the invention. Such modifications and variations are considered to be within the scope of the invention as defined by the claims.

[0300] Although various embodiments of the disclosed technologies have been described above, it should be understood that they are presented by way of example only and not as limitations. Similarly, various diagrams may depict example architectures or other configurations of the disclosed technologies, done to aid in understanding the features and functions that may be included in the disclosed technologies. The disclosed technologies are not limited to the illustrated example architectures or configurations, but various alternative architectures and configurations can be used to achieve the desired features. It will be apparent to those skilled in the art how alternative functions, logical or physical partitions and configurations can be implemented to achieve the desired features of the technologies disclosed herein. Furthermore, regarding flowcharts, descriptions of operations, and methods, the order of steps presented herein should not force the various embodiments to perform the listed functions in the same order, unless the context otherwise indicates.

[0301] Although the disclosed technology has been described above with reference to various exemplary embodiments and implementations, it should be understood that the various features, aspects, and functions described in one or more individual embodiments are not limited to their applicability to the particular embodiments in which they are described, but can be applied individually or in various combinations to one or more other embodiments of the disclosed technology, whether or not such features are presented as part of the described embodiments. Therefore, the breadth and scope of the technology disclosed herein should not be limited to any of the exemplary embodiments described above. As will become apparent to those skilled in the art upon reading this patent application, the illustrated embodiments and their various alternatives may be practiced without limitation to the illustrated examples. Example

[0302] Example 1: Design of a solid-state battery cell with ultra-long cycle life.

[0303] To provide the target performance for this example, we modeled the battery cell components shown in Table 1 to determine the target active material loading, electrode thickness, and solid electrolyte thickness, thereby achieving the desired energy density.

[0304] Table 1: Solid-state batteries with ultra-long cycle life

[0305] Battery cell components and design values

[0306]

[0307] Example 2: Lithium-ion battery cell with Li3PS4 solid electrolyte.

[0308] Li The DRS-LVO battery cell is assembled using a Li3PS4 solid electrolyte. The electrode composition is 40% DRS-LVO, 40% solid electrolyte, and 20% vapor-grown carbon fiber.

[0309] Figure 2A and Figure 2B An all-solid-state Li using Li3PS4 solid electrolyte is shown. Performance of DRS-LVO battery cells. Figure 2A The voltage characteristic curves of DRS-LVO at different rates at room temperature (approximately 25°C) are shown. Figure 2B The voltage characteristic curves of DRS-LVO at different rates at 60°C are shown. The voltage range is 0.01-2 V.

[0310] Room temperature testing results showed that DRS-LVO exhibited a reversible capacity of 200 mA·h / g at 0.5C, and retained only 16% (32 mA·h / g) of its capacity at 4.5C. Figure 2A Cell testing at 60°C showed that the DRS-LVO exhibited a high reversible capacity of 305 mA·h / g at 0.5C, and retained 53% (162 mA·h / g) and 25% (76 mA·h / g) of its capacity at 4.5C and 12C, respectively. Figure 2B ).

[0311] Example 3: Lithium-ion battery cell with Li6PS5Cl solid electrolyte.

[0312] Li The DRS-LVO battery cell is assembled using a Li6PS5Cl solid electrolyte. The electrode composition is 40% DRS-LVO, 40% solid electrolyte, and 20% vapor-grown carbon fiber.

[0313] Figure 3A , Figure 3Band Figure 3C An all-solid-state Li using Li6PS5Cl solid electrolyte is shown. Performance of DRS-LVO battery cells. Figure 3A The voltage characteristic curves of DRS-LVO at different rates at 60°C are shown. Figure 3B The cycling performance of DRS-LVO at 1C is shown. Figure 3C The voltage characteristic curves of the DRS-LVO at 1C for 200 cycles are shown. In this example, these batteries were tested at 60°C. The voltage range is 0.01–1.5 V.

[0314] The 60°C test results showed that at 60°C, DRS-LVO exhibited a reversible capacity of 259 mA·h / g at 1C, and retained 44% (113 mA·h / g) and 26% (67 mA·h / g) of its capacity at 12.5C and 25C, respectively. Figure 3A Regarding cycling performance, results at 60°C show that Li... The DRS-LVO battery cell experienced some degradation, with a capacity of 163 mA·h / g at 1C after 192 cycles. Figure 3B and Figure 3C This indicates that the operating voltage range of DRS-LVO in all-solid-state batteries can be further optimized. The capacity reduction in the early stages may be related to degradation at or near the electrolyte-anode material interface at 60°C, which can be addressed through material optimization.

[0315] Example 4: Lithium-ion battery cell with Li6PS5Cl solid electrolyte.

[0316] Li The DRS-LVO battery cell was assembled using a Li6PS5Cl solid electrolyte. The electrode composition was 40% DRS-LVO, 40% solid electrolyte, and 20% vapor-grown carbon fiber. In this example, the operating voltage window of the battery cell was narrowed to 0.01–1 V. The battery was tested at 60°C.

[0317] Figure 4A , Figure 4B and Figure 4C The all-solid-state Li using Li6PS5Cl solid electrolyte was described. Performance of DRS-LVO battery cells. Figure 4A The voltage characteristic curves of DRS-LVO at different rates at 60°C are shown. Figure 4B The cycling performance of DRS-LVO at 1C is shown (in Figure 4B In Chinese, "Cap" means capacity. Figure 4CThe voltage characteristic curve of DRS-LVO at 1C during 200 cycles is shown.

[0318] The 60°C test results showed that at 60°C, DRS-LVO exhibited a reversible capacity of 217 mA·h / g at 1C, and retained 34% (74 mA·h / g) and 18% (38 mA·h / g) of its capacity at 12.5C and 25C, respectively. Figure 4A Cycling results at 60°C show that Li The DRS-LVO battery cell initially undergoes some degradation, but then maintains a stable capacity of 143 mA·h / g after 200 cycles at 1C. Figure 4B and Figure 4C This indicates its long cycle life in all-solid-state batteries. Early-stage capacity reduction may be related to degradation at or near the electrolyte-anode material interface at 60°C, which can be addressed through material optimization.

[0319] Example 5: With Li 5.4 PS 4.4 Cl 1.6 Lithium-ion battery cells with solid electrolytes.

[0320] Li The DRS-LVO battery cell uses a lithium-rich silver-germanium sulfate electrolyte (LiCl). 5.4 PS 4.4 Cl 1.6 Assembly. The electrode composition is 40% DRS-LVO, 40% solid electrolyte, and 20% vapor-grown carbon fiber. The cell was tested at room temperature (approximately 25°C).

[0321] Figure 5A , Figure 5B and Figure 5C The use of Cl-rich lithium-sulfur silver-germanium ore electrolyte Li was demonstrated. 5.4 PS 4.4 Cl 1.6 All-solid-state Li Performance of DRS-LVO battery cells. Figure 5A The voltage characteristic curves of DRS-LVO at different rates at room temperature are shown. Figure 5B The cycling performance of DRS-LVO at 1C is shown. Figure 5C The voltage characteristic curve of DRS-LVO at 1C during 150 cycles is shown.

[0322] Room temperature testing results showed that DRS-LVO exhibited a reversible capacity of 282 mA·h / g at 1C and retained 27% (77 mA·h / g) of its capacity at 12.5C. Figure 5A These results at room temperature show that DRS-LVO exhibits almost no significant capacity reduction after 150 cycles at 1C. Figure 5B and Figure 5C This indicates its ultra-long cycle life in all-solid-state batteries. Using Li 5.4 PS 4.4 Cl 1.6 The cycle life under solid electrolyte conditions is surprisingly long.

[0323] Example 6: With Li 5.4 PS 4.4 Cl 1.6 Lithium-ion full battery cell with solid electrolyte.

[0324] DRS-LVO The NMC811 solid-state full cell uses a Cl-rich lithium-sulfur silver-germanium ore electrolyte. 5.4 PS 4.4 Cl 1.6 Assembly. The battery cell voltage window is 2.0-3.8 V, and the battery cell operates at a temperature of 60°C. Figure 6 The full-cell battery exhibits an average voltage of approximately 3.3 V.

Claims

1. A solid-state lithium-ion battery, comprising: An anode layer comprising lithium vanadium oxide, wherein the lithium vanadium oxide has a composition of Li a V b O c The given composition, where a = 0.001-10, b = 1-3, c = 1-9, and a, b, and c are chosen to balance the charge of the Li. a V b O c The Li a V b O c It can be reversibly lithiumized, and wherein the Li a V b O c At least some of them are in The space group has a disordered rock salt structure; A solid electrolyte layer, the solid electrolyte layer comprising a solid electrolyte; and Cathode layer, the cathode layer comprising cathode material, The solid electrolyte layer is inserted between the anode layer and the cathode layer.

2. The solid-state lithium-ion battery as described in claim 1, wherein, From about 0.01 wt% to 100 wt% of the Li a V b O c exist The space group has a disordered rock salt structure.

3. The solid-state lithium-ion battery as described in claim 1, wherein, The Li a V b O c Choose from the following groups: 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.

4. The solid-state lithium-ion battery as described in claim 1, wherein, The lithium vanadium oxide further contains a dopant M chemically or physically contained within the lithium vanadium oxide, such that its composition consists of Li a V b O c M d Given, where d = 0.001-3, where a, b, c and d are chosen to balance the charge of the Li. a V b O c M d The Li a V b O c M d It can be reversibly lithiumized, and wherein the Li a V b O c M d At least some of them are in The space group has a disordered rock salt structure.

5. The solid-state lithium-ion battery as described in claim 4, wherein, From about 0.01 wt% to 100 wt% of the Li a V b O c M d exist The space group has a disordered rock salt structure.

6. The solid-state lithium-ion battery as described in claim 4, wherein, The dopant M is selected from the group consisting of: Na, K, Be, Mg, Ca, Zn, Fe, Co, Ni, Cu, Ag, Sc, B, Y, Al, La, Si, Ge, Sn, Ti, Zr, Mn, P, Nb, Ta, Cr, Mo, W, Se, N, S, F, Cl, Br, I, and combinations thereof.

7. The solid-state lithium-ion battery as described in claim 1, wherein, The solid electrolyte is selected from the group consisting of: oxides, sulfides, phosphates, argentite, β-alumina, LISICON, garnet, NASICON, perovskite, anti-perovskite, lithium nitride, lithium hydride, lithium group 13 phosphides and lithium group 14 phosphides, lithium metal halides, LIPON, lithium thiophosphate, and combinations thereof.

8. The solid-state lithium-ion battery as described in claim 1, wherein, The solid electrolyte is a sulfur-based superionic conductor.

9. The solid-state lithium-ion battery as described in claim 8, wherein, The sulfur-based superionic conductor is a halogen-containing lithium-silver-germanium ore.

10. The solid-state lithium-ion battery as described in claim 9, wherein, The halogen-containing lithium-sulfur silver-germanium ore is selected from Li 6-ε PS 5-ε X 1+ε , where -1 < ε ≤ 1, and where X = F, Cl, Br, I, or a combination thereof.

11. The solid-state lithium-ion battery as claimed in claim 10, wherein, X = Cl, where 0 ≤ ε ≤ 0.

8.

12. The solid-state lithium-ion battery as described in claim 8, wherein, The sulfur-based superionic conductor is selected from the group consisting of: Li₂S-P₂S₅, Li₇P₃S 11 Li 10 GeP2S 12 Li7SiPS8, Li3PS4, Li 1+2x Zn 1-x PS4 (0 ≤ x < 1) and its combinations.

13. The solid-state lithium-ion battery as described in claim 1, wherein, The solid electrolyte is an oxide-based superionic conductor.

14. The solid-state lithium-ion battery as described in claim 13, wherein, The oxide-based superionic conductor is selected from the group consisting of: Li-Al2O3, Li7La3Zr2O 12 Li 2+2x Zn 1-x GeO4 (0 ≤ x ≤ 1), Li 1+x Zr2Si x P 3-x O 12 (0 < x < 3), La 2 / 3-x Li 3x TiO3 (0 < x < 2 / 3), Li x X 1 3X 2 2O 12 (X) 1 = La, Nd, Mg, or Ba; 2 = Te, Ta, Nb, Zr, or In; and 0 < x < 7), and their combinations.

15. The solid-state lithium-ion battery as described in claim 1, wherein, The solid electrolyte is a phosphate-based superionic conductor.

16. The solid-state lithium-ion battery as described in claim 15, wherein, The phosphate-based superionic conductor is selected from the group consisting of: Li3PO4, Li 1+x X 1 x X 2 2-x (PO4)3(X) 1 = Al, La, In, or Cr; X 2 = Ti, Ge, Zr, Hf, or Sn; and 0 < x < 2), and combinations thereof.

17. The solid-state lithium-ion battery as claimed in claim 1, wherein, The solid electrolyte is a nitride-based superionic conductor.

18. The solid-state lithium-ion battery of claim 17, wherein, The nitride-based superionic conductor is selected from the group consisting of: Li3N, Li x PO y N z (0 < x ≤ 3; 0 < y ≤ 4; and 0 < z ≤ 1), and their combinations.

19. The solid-state lithium-ion battery as claimed in claim 1, wherein, The solid electrolyte is a superionic conductor based on hydrides.

20. The solid-state lithium-ion battery as claimed in claim 19, wherein, The hydride-based superionic conductor is selected from the group consisting of: LiBH4, LiCB9H 10 LiCB 11 H 12 , and their combinations.

21. The solid-state lithium-ion battery as described in claim 7, wherein, The anti-perovskite is selected from the group consisting of: Li3OCl, Li3OBr, Li3OF, Li3OI, and combinations thereof.

22. The solid-state lithium-ion battery as described in claim 1, wherein, The cathode material is selected from the group consisting of: LiCoO2, LiMn2O4, Li2MnO3, LiFePO4, and LiNi. x Co y Al z O2 (x + y + z = 1), LiMn x Ni y O4 (x + y = 2), LiNi x Co y Mn z O2 (x + y + z = 1), LiFe x Mn y PO4 (x + y = 1), aLiNi x Co y Mn z O2∙(1-a)Li2MnO3 (0 < a < 1 and x + y + z = 1), and its combinations.

23. The solid-state lithium-ion battery as described in claim 22, wherein, The cathode material is LiNi. x Co y Mn z O2.

24. The solid-state lithium-ion battery as described in claim 23, wherein, The LiNi x Co y Mn z O2 is LiNi 0.8 Co 0.1 Mn 0.1 O2.

25. The solid-state lithium-ion battery as claimed in claim 1, wherein, The solid electrolyte is also contained within the anode layer.

26. The solid-state lithium-ion battery as claimed in claim 1, wherein, The solid electrolyte is also contained within the cathode layer.

27. The solid-state lithium-ion battery as claimed in claim 1, wherein, The anode layer, the cathode layer, or the solid electrolyte layer further contains a noble metal in neutral or ionic form, wherein the noble metal is optionally selected from the group consisting of Au, Ag, Pt, Rh, Pd, Ru, Os, Ir, and combinations thereof.

28. The solid-state lithium-ion battery as claimed in claim 1, wherein, The anode layer further comprises a second anode material selected from the group consisting of: silicon, silicon oxide, graphite, hard carbon, soft carbon, silicon-carbon composites, aluminum, magnesium, zinc, tin, tin oxide, and combinations thereof.

29. The solid-state lithium-ion battery as claimed in claim 1, wherein, The anode layer further contains sp in the form of sp. 2 Form and / or sp 3 Anode carbon additives in various forms.

30. The solid-state lithium-ion battery as described in claim 29, wherein, The anode carbon additive is graphite, graphene, carbon nanotubes, carbon fibers, ultrafine carbon, activated carbon, carbon black, nanodiamond, hard carbon, soft carbon, or a combination thereof.

31. The solid-state lithium-ion battery as described in claim 1, wherein, The cathode layer further contains sp-formed ... 2 Form and / or sp 3 Cathode carbon additives in various forms.

32. The solid-state lithium-ion battery as described in claim 31, wherein, The cathode carbon additive is graphite, graphene, carbon nanotubes, carbon fibers, ultrafine carbon, activated carbon, carbon black, nanodiamond, hard carbon, soft carbon, or a combination thereof.

33. The solid-state lithium-ion battery as described in claim 1, wherein, The cathode layer is disposed on the cathode current collector, and the anode layer is disposed on the anode current collector.

34. The solid-state lithium-ion battery as described in claim 1, wherein, The solid-state lithium-ion battery comprises multiple anode layers, multiple solid electrolyte layers, and multiple cathode layers.

35. The solid-state lithium-ion battery as described in claim 1, wherein, The solid-state lithium-ion battery retains at least 80% of its capacity after 20,000 cycles.

36. The solid-state lithium-ion battery as described in claim 1, wherein, The solid-state lithium-ion battery can be charged to 80% state of charge in 3 minutes or less.

37. The solid-state lithium-ion battery as claimed in claim 1, wherein, The solid-state lithium-ion battery has an energy density of at least 200 W·h / kg.

38. The solid-state lithium-ion battery as described in claim 1, wherein, The solid-state lithium-ion battery has an energy density of at least 650 W·h / L.

39. The solid-state lithium-ion battery as claimed in claim 1, wherein, The solid-state lithium-ion battery is capable of operating in a temperature range of approximately -80°C to approximately 350°C.

40. The solid-state lithium-ion battery as claimed in claim 1, wherein, The solid-state lithium-ion battery does not experience lithium metal deposition during operation.

41. The solid-state lithium-ion battery as described in claim 1, wherein, The solid-state lithium-ion battery is contained within a battery module / group that includes multiple batteries.

42. The solid-state lithium-ion battery as described in claim 41, wherein, The battery module / pack is included in the electric vehicle.

43. The solid-state lithium-ion battery as described in claim 42, wherein, The electric vehicle in question is an electric car.

44. The solid-state lithium-ion battery as described in claim 42, wherein, The electric vehicle is an electric truck or bus.

45. The solid-state lithium-ion battery as described in claim 42, wherein, The electric vehicle in question is an electric motor vehicle.

46. ​​The solid-state lithium-ion battery as described in claim 42, wherein, The electric vehicle in question is an electric aircraft.

47. The solid-state lithium-ion battery as claimed in claim 1, wherein, The solid-state lithium-ion battery is contained within the portable device.

48. The solid-state lithium-ion battery as claimed in claim 1, wherein, The solid-state lithium-ion battery is contained within the smart device.

49. The solid-state lithium-ion battery as claimed in claim 1, wherein, The solid-state lithium-ion battery is included in the emergency power backup system.

50. The solid-state lithium-ion battery as claimed in claim 1, wherein, The solid-state lithium-ion battery is included within the solar power storage system.

51. A method for manufacturing a battery cell, the method comprising: (a) Casting an anode material, an anode carbon additive, and a solid electrolyte onto a first substrate to form an anode, wherein the anode material comprises a plurality of anode material particles, wherein the anode particles contain Li x V y O z The inner phase, where x = 0-10, y = 1-3, z = 1-9, and x, y, and z are chosen to balance the charge of the Li. x V y O z ; (b) The Li foil is compacted onto the anode to form a compacted anode; (c) Casting the cathode material, cathode carbon additive and the solid electrolyte onto a second substrate to form a cathode; (d) Stacking a solid electrolyte layer onto the compacted anode, wherein the solid electrolyte layer contains the solid electrolyte; (e) Stacking the cathode onto the solid electrolyte layer; (f) Enclosing the plurality of said anode layers, the plurality of said solid electrolyte layers, and the plurality of said cathode layers with foil to form a battery cell; as well as (g) Converting the compacted anode into a lithium-ionized anode, the lithium-ionized anode comprising Li a V b O c Where a = 0.001-10, b = 1-3, c = 1-9, and a, b, and c are chosen to balance the charge of the Li. a V b O c The Li a V b O c It can be reversibly lithiumized, and wherein the Li a V b O c At least some of them are in The space group has a disordered rock salt structure.

52. The method of claim 51, wherein, The anode material particles further contain a dopant M chemically or physically contained within the anode material particles, to have a composition of Li a V b O c M d The given composition, where d = 0.001-3, is used where a, b, c, and d are chosen to balance the charge of the Li. a V b O c M d The Li a V b O c M d It can be reversibly lithiumized, and wherein the Li a V b O c M d At least some of them are in The space group has a disordered rock salt structure.

53. The method of claim 51, wherein, The anode material, the anode carbon additive, and the solid electrolyte are coated on both sides of a layer of the first substrate; and the cathode material, the cathode carbon additive, and the solid electrolyte are coated on both sides of a layer of the second substrate.

54. The method of claim 51, wherein, Step (a) uses a casting pressure selected from about 10 kPa to about 100 MPa.

55. The method of claim 51, wherein, Step (b) uses a compaction pressure selected from about 1 MPa to about 100 MPa.

56. The method of claim 51, wherein, The first substrate is a copper foil having a thickness of about 1 micrometer to about 100 micrometers.

57. The method of claim 51, wherein, The second substrate is an aluminum foil with a thickness of about 1 micrometer to about 100 micrometers.

58. The method of claim 51, wherein, The anode has an anode material loading selected from about 20 wt% to about 100 wt%.

59. The method of claim 51, wherein, The anode has a concentration of about 0.2 mg / cm³ on at least one side of the anode. 2 Approximately 50 mg / cm 2 Anode material surface load.

60. The method of claim 51, wherein, The anode has a density selected from about 0.05 mA·h / cm on at least one side of the anode. 2 Approximately 10 mA·h / cm 2 The areal capacity of the anode material.

61. A method for manufacturing a battery cell, the method comprising: (a) Casting an anode material, an anode carbon additive, and a solid electrolyte onto a first substrate to form an anode, wherein the anode material comprises a plurality of anode material particles, wherein the anode particles contain Li a V b O c The inner phase, wherein a = 0.001–10, b = 1–3, c = 1–9, and a, b, and c are chosen to balance the charge of the Li. a V b O c ; (b) Casting the cathode material, cathode carbon additive and the solid electrolyte onto a second substrate to form a cathode; (c) Stacking a solid electrolyte layer onto the anode, wherein the solid electrolyte layer contains the solid electrolyte; (d) Stack the cathode onto the solid electrolyte layer; as well as (e) Enclosing the plurality of said anode layers, the plurality of said solid electrolyte layers, and the plurality of said cathode layers with foil to form a battery cell. The Li a V b O c It can be reversibly lithiumized, and wherein the Li a V b O c At least some of them are in The space group has a disordered rock salt structure.

62. The method of claim 61, wherein, The anode material particles further contain a dopant M chemically or physically contained within the anode material particles, to have a composition of Li a V b O c M d The given composition, where d = 0.001-3, is used where a, b, c, and d are chosen to balance the charge of the Li. a V b O c M d The Li a V b O c M d It can be reversibly lithiumized, and wherein the Li a V b O c M d At least some of them are in The space group has a disordered rock salt structure.

63. The method of claim 61, wherein, The anode material, the anode carbon additive, and the solid electrolyte are coated on both sides of the layer of the first substrate.

64. The method of claim 61, wherein, The cathode material, the cathode carbon additive, and the solid electrolyte are coated on both sides of the layer of the second substrate.

65. The method of claim 61, wherein, Step (a) uses a casting pressure selected from about 10 kPa to about 100 MPa.

66. The method of claim 61, wherein, The first substrate is a copper foil having a thickness of about 1 micrometer to about 100 micrometers.

67. The method of claim 61, wherein, The second substrate is an aluminum foil with a thickness of about 1 micrometer to about 100 micrometers.

68. The method of claim 61, wherein, The anode has an anode material loading selected from about 20 wt% to about 100 wt%.

69. The method of claim 61, wherein, The anode has a concentration of about 0.2 mg / cm³ on at least one side of the anode. 2 Approximately 50 mg / cm 2 Anode material surface load.

70. The method of claim 61, wherein, The anode has a density selected from about 0.05 mA·h / cm on at least one side of the anode. 2 Approximately 10 mA·h / cm 2 The areal capacity of the anode material.

71. A method for manufacturing a battery cell, the method comprising: (a) Casting an anode material, an anode carbon additive, a solid electrolyte, and Li metal onto a first substrate to form an anode, wherein the anode material comprises a plurality of anode material particles, wherein the anode particles contain Li x V y O z The inner phase, where x = 0-10, y = 1-3, z = 1-9, and x, y, and z are chosen to balance the charge of the Li. x V y O z ; (b) Casting the cathode material, cathode carbon additive and the solid electrolyte onto a second substrate to form a cathode; (c) Stacking a solid electrolyte layer onto the anode, wherein the solid electrolyte layer contains the solid electrolyte; (d) Stack the cathode onto the solid electrolyte layer; (e) Enclosing the plurality of said anode layers, the plurality of said solid electrolyte layers, and the plurality of said cathode layers with foil to form a battery cell; as well as (f) Converting the anode into a lithium-ion anode, the lithium-ion anode comprising Li a V b O c Where a = 0.001-10, b = 1-3, c = 1-9, and a, b, and c are chosen to balance the charge of the Li. a V b O c The Li a V b O c It can be reversibly lithiumized, and wherein the Li a V b O c At least some of them are in The space group has a disordered rock salt structure.

72. The method of claim 71, wherein, The Li metal is selected from the group consisting of: Li metal powder, Li metal ingot, Li metal foil, and combinations thereof.

73. The method of claim 71, wherein, The anode material particles further contain a dopant M chemically or physically contained within the anode material particles, to have a composition of Li a V b O c M d The given composition, where d = 0.001-3, is used where a, b, c, and d are chosen to balance the charge of the Li. a V b O c M d The Li a V b O c M d It can be reversibly lithiumized, and wherein the Li a V b O c M d At least some of them are in The space group has a disordered rock salt structure.

74. The method of claim 71, wherein, The anode material, the anode carbon additive, and the solid electrolyte are coated on both sides of the layer of the first substrate.

75. The method of claim 71, wherein, The cathode material, the cathode carbon additive, and the solid electrolyte are coated on both sides of the layer of the second substrate.

76. The method of claim 71, wherein, Step (a) uses a casting pressure selected from about 10 kPa to about 100 MPa.

77. The method of claim 71, wherein, The first substrate is a copper foil having a thickness of about 1 micrometer to about 100 micrometers, and the second substrate is an aluminum foil having a thickness of about 1 micrometer to about 100 micrometers.

78. The method of claim 71, wherein, The anode has an anode material loading selected from about 20 wt% to about 100 wt%.

79. The method of claim 71, wherein, The anode has a concentration of about 0.2 mg / cm³ on at least one side of the anode. 2 Approximately 50 mg / cm 2 Anode material surface load.

80. The method of claim 71, wherein, The anode has a density selected from about 0.05 mA·h / cm on at least one side of the anode. 2 Approximately 10 mA·h / cm 2 The areal capacity of the anode material.

81. A method for manufacturing a battery cell, the method comprising: (a) Casting an anode material, an anode carbon additive, and a solid electrolyte onto a first substrate to form an anode, wherein the anode material comprises a plurality of anode material particles, wherein the anode particles contain Li x V y O z The inner phase, where x = 0-10, y = 1-3, z = 1-9, and x, y, and z are chosen to balance the charge of the Li. x V y O z ; (b) Casting cathode material, cathode carbon additive, the solid electrolyte and lithium-containing compound onto a second substrate to form a cathode, wherein the lithium-containing compound is chemically different from the cathode material; (c) Stacking a solid electrolyte layer onto the anode; (d) Stack the cathode onto the solid electrolyte layer; (e) Enclosing the plurality of said anode layers, the plurality of said solid electrolyte layers, and the plurality of said cathode layers with foil to form a battery cell; as well as (f) Decomposing the lithium-containing compound to add lithium to the anode material particles, thereby converting the anode into a lithiated anode, the lithiated anode comprising Li a V b O c Where a = 0.001-10, b = 1-3, c = 1-9, and a, b, and c are chosen to balance the charge of the Li. a V b O c The Li a V b O c It can be reversibly lithiumized, and wherein the Li a V b O c At least some of them are in The space group has a disordered rock salt structure.

82. The method of claim 81, wherein, The anode material particles further contain a dopant M chemically or physically contained within the anode material particles, to have a composition of Li a V b O c M d The given composition, where d = 0.001-3, is used where a, b, c, and d are chosen to balance the charge of the Li. a V b O c M d The Li a V b O c M d It can be reversibly lithiumized, and wherein the Li a V b O c M d At least some of them are in The space group has a disordered rock salt structure.

83. The method of claim 81, wherein, The lithium-containing compound is selected from the group consisting of: lithium oxide, lithium hydride, lithium hydroxide, lithium hydroperoxide, lithium peroxide, lithium nitride, lithium carbonate, lithium bicarbonate, lithium sulfide, lithium sulfate, lithium squaric acid, lithium oxalate, lithium ketone malonate, lithium diketone succinate, and combinations thereof.

84. The method of claim 83, wherein, The lithium-containing compound is lithium oxide and / or lithium nitride.

85. The method of claim 81, wherein, The anode material, the anode carbon additive, and the solid electrolyte are coated on both sides of a layer of the first substrate; and the cathode material, the cathode carbon additive, and the solid electrolyte are coated on both sides of a layer of the second substrate.

86. The method of claim 81, wherein, Step (a) uses a casting pressure selected from about 10 kPa to about 100 MPa.

87. The method of claim 81, wherein, The first substrate is a copper foil having a thickness of about 1 micrometer to about 100 micrometers.

88. The method of claim 81, wherein, The second substrate is an aluminum foil with a thickness of about 1 micrometer to about 100 micrometers.

89. The method of claim 81, wherein, The anode has an anode material loading selected from about 20 wt% to about 100 wt%.

90. The method of claim 81, wherein, The anode has a concentration of about 0.2 mg / cm³ on at least one side of the anode. 2 Approximately 50 mg / cm 2 Anode material surface load.

91. The method of claim 81, wherein, The anode has a density selected from about 0.05 mA·h / cm on at least one side of the anode. 2 Approximately 10 mA·h / cm 2 The areal capacity of the anode material.

92. The method of claim 81, wherein, Step (f) is performed before the battery cell is charged.

93. The method of claim 81, wherein, Step (f) is performed during the charging of the battery cell.

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