Solid-state battery cell, battery device, and power-using device
Patent Information
- Application Number
- CN202611284476.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-08-23
- Publication Date
- 2026-10-27
AI Technical Summary
但是依然难以满足下一代高能量密度全固态电池的需求
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Figure CN122991983A_ABST
Abstract
Description
Technical Field
[0001] This application relates to a solid-state battery cell, a battery device, and an electrical device. Background Technology
[0002] Compared to liquid battery cells that typically use liquid electrolytes, solid-state battery cells, due to their use of solid electrolyte materials, are less prone to combustion and explosion, and offer high reliability and high energy density. However, they still fall short of meeting the demands of next-generation high-energy-density all-solid-state batteries. Summary of the Invention
[0003] This application provides a solid-state battery cell, a battery device, and an electrical device. The first active material has reversible redox activity and a matching voltage platform with the second active material. As a hybrid electrode active material, the solid-state battery cell can have good cycle performance and high capacity.
[0004] In a first aspect, embodiments of this application provide a solid-state battery cell, comprising a positive electrode, a negative electrode, and an electrolyte layer, wherein the electrolyte layer is located between the negative electrode and the positive electrode. At least one of the positive electrode and the negative electrode comprises an electrode current collector and an electrode film layer located on at least one side of the electrode current collector. The electrode film layer comprises an electrode active material, which comprises a first active material and a second active material. The charge / discharge voltage range of the first active material intersects with the charge / discharge voltage range of the second active material. The first active material comprises one or more compounds with a structure of Li-MX and a structure of Li-MXA, wherein M comprises one of Fe, Mo, W, Nb, Ta, Zr, V, In, Sc, Y, Ga, and Ln, X comprises one or more of F, Cl, Br, and I, and A comprises O, N, S, and PO4. 3 CO3 2 SiO4 4 SO4 2 C2O4 2 BO2 ClO4 P2O7 4 BF4 and OH One or more of them.
[0005] The first active material of this application has reversible redox activity, which can contribute to the capacity. At the same time, the charge-discharge voltage range of the first active material overlaps with that of the second active material, which allows the first active material to undergo lithiation / delithiation reactions simultaneously with the second active material during the charge-discharge process of the battery cell, thereby contributing additional capacity without sacrificing ion conduction function.
[0006] Therefore, using the first and second active materials as hybrid electrode active materials can enable solid-state battery cells to have high capacity and good cycle performance.
[0007] In some embodiments, the overlap between the charge / discharge voltage range of the first active material and the charge / discharge voltage range of the second active material is greater than 50%.
[0008] In some embodiments, the charge / discharge voltage range of the first active material is 0.1–4.2 V.
[0009] In some embodiments, the charge / discharge voltage range of the second active material is 0–5 V.
[0010] In some embodiments, when the electrode active material is a positive electrode active material, the charge / discharge voltage range of the first active material is 0.1–4.2 V, and the charge / discharge voltage range of the second active material is 2–5 V.
[0011] In some embodiments, when the electrode active material is a negative electrode active material, the charge-discharge voltage range of the first active material is 0.1–4.2 V, and the charge-discharge voltage range of the second active material is 0–2.5 V.
[0012] In some embodiments, the mass ratio of the first active material to the second active material in the electrode film is 5:95–50:50.
[0013] In some embodiments, the first active material includes Li2FeCl4, Li 1.3 Fe 1.2 One or more of the following: Cl4, Li3VCl6, Li3TiCl6, Li2ZrCl6, Li3InCl6, LiTaCl6, Li2ZrOCl4, LiNbOCl4, and Li2CO3-TaCl5.
[0014] In some embodiments, when the electrode active material is a positive electrode active material, the second active material includes one or more of lithium transition metal oxides and their modified materials, lithium phosphates and their modified materials, and conversion-type positive electrodes.
[0015] In some embodiments, the lithium transition metal oxide includes one or more of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, and lithium-rich manganese-based materials; the lithium-containing phosphate includes one or more of lithium iron phosphate, lithium iron phosphate and carbon composites, lithium manganese phosphate, lithium manganese phosphate and carbon composites, lithium manganese iron phosphate, and lithium manganese iron phosphate and carbon composites; and the conversion cathode includes one or more of sulfur, sulfur and carbon composites, selenium, selenium and carbon composites, iodine, iodine and carbon composites, metal sulfides, metal selenides, and metal halides.
[0016] In some embodiments, when the electrode active material is a negative electrode active material, the second active material includes one or more of lithium, lithium alloy, natural graphite, artificial graphite, mesophase micro carbon spheres, soft carbon, hard carbon, silicon-based materials, tin-based materials, phosphorus-based materials, lithium titanate, and metal oxides.
[0017] In some embodiments, when the M element in the first active material includes one or more of Fe, Mo, W, Nb, Ta, V, In, Yb, Eu, and Ga, the second active material includes a lithium transition metal oxide.
[0018] In some embodiments, when the M element in the first active material includes one or more of Fe, Mo, W, Nb, Ta, V, In, Yb, Eu, and Ga, the second active material includes a lithium phosphate.
[0019] In some embodiments, when the M element in the first active material includes one or more of Zr, Yb, Ta, Ga, and W, the second active material includes lithium titanate.
[0020] In some embodiments, when the M element in the first active material includes one or more of Zr, Yb, Ta, Ga, and W, the second active material includes sulfur.
[0021] In some embodiments, when the M element in the first active material includes one or more of Y, Sc, and Ln, the second active material includes one or more of lithium alloy, natural graphite, artificial graphite, mesophase microcarbon spheres, soft carbon, hard carbon, silicon-based materials, tin-based materials, and phosphorus-based materials.
[0022] Secondly, embodiments of this application provide a battery device including the solid-state battery cell described in the first aspect.
[0023] Thirdly, embodiments of this application provide an electrical device, including a solid-state battery cell as described in the first aspect or a battery device as described in the second aspect. Attached Figure Description
[0024] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments of this application will be briefly introduced below. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0025] Figure 1 This is a schematic diagram showing the matching of the charge / discharge voltages of the first active material and the second active material in this application. Detailed Implementation
[0026] To better understand the above-mentioned objectives, features, and advantages of this application, the solution of this application will be further described below. It should be noted that, unless otherwise specified, the embodiments and features described in these embodiments can be combined with each other.
[0027] Many specific details are set forth in the following description in order to provide a full understanding of this application, but this application may also be implemented in other ways different from those described herein; obviously, the embodiments in the specification are only some embodiments of this application, and not all embodiments.
[0028] The following detailed description, with appropriate reference to the accompanying drawings, specifically discloses embodiments of the solid-state battery cell, battery device, and power-consuming device of this application. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of practically identical structures may be omitted. This is to avoid unnecessarily lengthy descriptions and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided for the purpose of enabling those skilled in the art to fully understand this application and are not intended to limit the subject matter of the claims.
[0029] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also included. Furthermore, if minimum range values of 1 and 2 are listed, and if maximum range values of 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
[0030] Unless otherwise specified, all embodiments and optional embodiments of this application may be combined with each other to form new technical solutions, and such technical solutions should be considered to be included in the disclosure of this application.
[0031] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions, and such technical solutions shall be deemed to be included in the disclosure of this application.
[0032] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the method may also include step (c), indicating that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.
[0033] Unless otherwise specified, in this application, the terms "first," "second," etc., are used to distinguish different objects, rather than to describe a specific order or primary / secondary relationship.
[0034] In this application, the terms "multiple" or "various" refer to two or more kinds of things.
[0035] In the description of the embodiments of this application, unless otherwise specified, "above" or "below" the second feature can mean that the first feature is in direct contact with the second feature, or that the first feature is in indirect contact with the second feature through an intermediate medium. Furthermore, "above," "over," and "on top" can mean that the first feature is directly above or diagonally above the second feature, or simply that the first feature is at a higher horizontal level than the second feature. "Below," "below," and "under" the second feature can mean that the first feature is directly below or diagonally below the second feature, or simply that the first feature is at a lower horizontal level than the second feature.
[0036] Unless otherwise stated, the test temperature for all parameters mentioned in this application is 25°C.
[0037] The solid-state battery cells mentioned in the embodiments of this disclosure are capable of charging and discharging independently. Solid-state battery cells may be cylindrical, cuboid, or other shapes, and the embodiments of this disclosure are not limited in this respect.
[0038] The battery apparatus mentioned in the embodiments of this disclosure may include one or more battery cell assemblies for providing voltage and capacity. A battery cell assembly may include multiple solid-state battery cells, which are connected in series, parallel, or mixed connections via busbars.
[0039] In some embodiments, a battery cell assembly is typically formed by arranging multiple solid-state battery cells.
[0040] As an example, a battery cell assembly can be a battery module, which consists of multiple solid-state battery cells arranged and fixed together to form an independent module. As another example, a battery module can be formed by bundling multiple solid-state battery cells together with cable ties.
[0041] In some embodiments, the battery device may be a battery pack, which includes a housing and one or more individual battery cells housed within the housing.
[0042] As an example, the battery cell assembly can be a battery module, and the battery cell assembly can be housed in the housing by fixing the battery module in the housing.
[0043] As an example, battery cell assemblies can also be housed in a housing by directly fixing multiple solid-state battery cells to the housing.
[0044] As an example, the enclosure may include a first enclosure and a second enclosure. The first enclosure and the second enclosure are fastened together to form a closed space inside the enclosure to house the individual battery cells. Here, "closed" refers to covering or closing, and can be either sealed or unsealed. The first enclosure may be a top cover or a bottom plate.
[0045] As an example, the enclosure may include a top cover, a frame, and a bottom plate. The top cover and bottom plate are connected to the frame, creating an enclosed space inside the enclosure to house the individual battery cells.
[0046] In some embodiments, the housing may be part of the vehicle's chassis structure. For example, a portion of the housing may be at least a part of the vehicle's floor, or a portion of the housing may be at least a part of the vehicle's crossbeams and longitudinal beams.
[0047] The technical solutions described in this disclosure are applicable to various electrical devices that use solid-state battery cells or battery devices, such as, but not limited to, mobile devices (e.g., mobile phones, tablets, laptops, etc.), electric vehicles (e.g., pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc. Solid-state battery cells and battery devices are used to store or provide electrical energy.
[0048] The solid-state battery cells disclosed herein may include rigid-case solid-state battery cells, pouch solid-state battery cells, etc.
[0049] All-solid-state batteries, by using non-flammable solid electrolytes instead of liquid electrolytes, possess the potential for high safety and high energy density, making them an important development direction for next-generation energy storage technology. However, in current all-solid-state battery designs, the solid electrolyte is mostly used only as an ion-conducting medium added to the electrode film. This portion constitutes "dead mass" in the total mass of the battery cell, contributing no capacity and directly limiting further improvements in the energy density of solid-state batteries. Although some studies have reported the use of certain halides containing redox-resistant transition metal elements as electrode active materials, their capacity depends entirely on the redox reaction of the central transition metal cation (such as Ti). 2+ / Ti 3+ V 2+ / V 3 + The voltage plateau of this type of cation redox is usually low, and the theoretical capacity is also low, making it difficult to meet the needs of next-generation high-energy-density all-solid-state batteries.
[0050] In view of this, embodiments of this application provide a solid-state battery cell, a battery device, and an electrical device. The first active material has reversible redox activity and a matching voltage platform with the second active material. As a hybrid electrode active material, the solid-state battery cell can have high capacity and good cycle performance.
[0051] At least one of the positive and negative electrodes provided in this application includes an electrode current collector and an electrode film layer located on at least one side of the electrode current collector. The electrode film layer includes an electrode active material, which includes a first active material and a second active material. The charge / discharge voltage range of the first active material and the charge / discharge voltage range of the second active material overlap. The first active material includes one or more compounds with the structure Li-MX and Li-MXA, wherein M includes one of Fe, Mo, W, Nb, Ta, Zr, V, In, Sc, Y, Ga, and Ln, X includes one or more of F, Cl, Br, and I, and A includes O, N, S, and PO4. 3 CO3 2 SiO4 4 SO4 2 C2O4 2 BO2 ClO4 P2O7 4 BF4 and OH One or more of them.
[0052] In this application, Ln refers to a lanthanide element, including one or more of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
[0053] The first active material of this application has reversible redox activity, which can contribute to the capacity. At the same time, the charge-discharge voltage range of the first active material overlaps with that of the second active material, which allows the first active material to undergo lithiation / delithiation reactions simultaneously with the second active material during the charge-discharge process of the battery cell, thereby contributing additional capacity without sacrificing ion conduction function.
[0054] Therefore, using the first and second active materials as hybrid electrode active materials can enable solid-state battery cells to have high capacity and good cycle performance.
[0055] Optionally, the first active material comprises one or more compounds with the structure Li-MXA, wherein M comprises one of Fe, Mo, W, Nb, Ta, Zr, V, In, Yb, Eu, Sc, Y, Ga, and Ln, X comprises one or more of F, Cl, Br, and I, and A comprises O, N, S, and PO4. 3 CO3 2 SiO4 4 SO4 2 C2O4 2 BO2 ClO4 P2O7 4 BF4 and OH One or more of them.
[0056] There is a risk of loss of the redox products of the first active material, which could lead to the structural collapse of the first active material and worsen its reversibility.
[0057] This application describes a Li-MXA compound containing the element A, which can bind redox products and improve the reversibility of redox reactions. A is PO4. 3 CO3 2 SiO4 4 SO4 2 C2O4 2 BO2 ClO4 P2O7 4 and BF4 When one or more of the following are present, the first active material is a polyanionic halide.
[0058] In some embodiments, the overlap between the charge / discharge voltage range of the first active material and the charge / discharge voltage range of the second active material is greater than 50%, for example, greater than 60%, greater than 70%, greater than 80%, greater than 90%, or greater than 99%.
[0059] In this application, the overlap ratio refers to the ratio of the length of the overlapping segment between the charge / discharge voltage range of the first active material and the charge / discharge voltage range of the second active material to the length of the charge / discharge voltage range of the first active material. For example, if the charge / discharge voltage range of the first active material is from a to b, then the corresponding length is ba, denoted as α; if the charge / discharge voltage range of the second active material is from A to B, then the corresponding length is BA, denoted as β. The overlap ratio is then |β-α| / α.
[0060] The high overlap of the redox plateau voltages of the first and second active materials in this application allows for better synchronous lithiation / delithiation reactions, thus improving the capacity of solid-state battery cells.
[0061] In some embodiments, the charge / discharge voltage range of the first active material is 0.1–4.2 V, for example, it can be 0.1 V, 0.2 V, 0.3 V, 0.4 V, 0.5 V, 0.6 V, 0.7 V, 0.8 V, 0.9 V, 1.0 V, 1.1 V, 1.2 V, 1.3 V, 1.4 V, 1.5 V, 1.6 V, 1.7 V, 1.8 V, 1.9 V, 2.0 V, 2.1 V, 2.2 V, 2.3 V, 2.4 V, 2.5 V, 2.6 V, 2.7 V, 2.8 V, 2.9 V, 3.0 V, 3.1 V, 3.2 V, 3.3 V, 3.4 V, 3.5 V, 3.6 V, 3.7 V, 3.8 V, 3.9 V, 4.0 V, 4.1 V, 4.2 V, or any range of the above values.
[0062] In some embodiments, the charge / discharge voltage range of the second active material is 0–5 V, for example, it can be 0, 0.1 V, 0.2 V, 0.3 V, 0.4 V, 0.5 V, 0.6 V, 0.7 V, 0.8 V, 0.9 V, 1.0 V, 1.1 V, 1.2 V, 1.3 V, 1.4 V, 1.5 V, 1.6 V, 1.7 V, 1.8 V, 1.9 V, 2.0 V, 2.1 V, 2.2 V, 2.3 V, 2.4 V, 2.5 V, 2.6 V, 2.7 V, 2.8 V, 2.9 V, 3.0 V, 3.1 V, 3.2 V, 3.3 V, 3.4 V, 3.5 V, 3.6 V, 3.7 V, 3.8 V, 3.9 V, 4.0 V, 4.1 V, 4.2 V, 4.3 V, 4.4 V, 4.5 V. V, 4.6 V, 4.7 V, 4.8 V, 4.9 V, 5.0 V, or any range of the above values.
[0063] In some embodiments, when the electrode active material is a positive electrode active material, the charge / discharge voltage range of the first active material is 0.1–4.2 V, and the charge / discharge voltage range of the second active material is 2–5 V.
[0064] The first and second active materials of this application have the aforementioned redox plateau voltage, which enables solid-state battery cells to have high capacity and better cycle performance.
[0065] In some embodiments, when the electrode active material is a negative electrode active material, the charge-discharge voltage range of the first active material is 0.1–4.2 V, and the charge-discharge voltage range of the second active material is 0–2.5 V.
[0066] The first and second active materials of this application have the aforementioned redox plateau voltage, which enables solid-state battery cells to have high capacity and better cycle performance.
[0067] In some embodiments, the mass ratio of the first active material to the second active material in the electrode film is 5:95-50:50, for example, it can be 5:95, 10:90, 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, or any range of the above values.
[0068] The first active material and the second active material have the above-mentioned mass ratio, which can better utilize the capacity of both materials and also take into account the ion transport performance, so that the solid-state battery cell can better achieve both higher capacity and better cycle performance.
[0069] [positive electrode] In some embodiments, the positive electrode includes a positive current collector and a positive electrode film layer located on at least one side of the positive current collector, the positive electrode film layer including a positive electrode active material.
[0070] In some embodiments, the positive current collector may be a metal foil or a composite current collector. The metal foil may be a pure metal, an alloy, or a surface-treated metal, such as, but not limited to, stainless steel foil, carbon-coated aluminum foil, or aluminum foil. The composite current collector may include a polymer substrate and a metal layer formed on at least one surface of the polymer substrate. As an example, the metal material may include, but is not limited to, one or more of aluminum, aluminum alloys, nickel, nickel alloys, titanium, titanium alloys, silver, and silver alloys. As an example, the polymer substrate may include, but is not limited to, one or more of polypropylene, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), and polyethylene.
[0071] In some embodiments, to further improve the energy density of a solid-state battery cell, the positive electrode active material may include materials of the general formula Li. a Ni b Co c M d O e A f One or more of lithium transition metal oxides and their modified materials. 0.8≤a≤1.2, 0.5≤b<1, 0<c<1, 0<d<1, 1≤e≤2, 0≤f≤1, M may include one or more of Mn, Al, Zr, Zn, Cu, Cr, Mg, Fe, V, Ti, and B, and A may include one or more of N, F, S, and Cl. Optionally, 0.6≤b<1, 0.8≤b<1.
[0072] As an example, the positive electrode active material may include, but is not limited to, LiCoO2, LiNiO2, LiMnO2, LiMn2O4, and LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2 (abbreviated as NCM111), LiNi 0.5 Co 0.2 Mn 0.3 O2 (abbreviated as NCM523), LiNi 0.5 Co 0.25 Mn 0.25 O2 (abbreviated as NCM211), LiNi 0.6 Co 0.2 Mn 0.2 O2 (abbreviated as NCM622), LiNi 0.8 Co 0.1 Mn 0.1 O2 (abbreviated as NCM811), LiNi 0.83 Co 0.12 Mn 0.05 O2 (abbreviated as NCM83), LiNi 0.9 Co 0.05 Mn 0.05 O2 (NCM90), LiNi 0.92 Co 0.04 Mn 0.04 O2 (NCM92), LiNi 0.93 Co 0.035 Mn 0.035 O2 (NCM93), LiNi 0.96 Co 0.02 Mn 0.02 O2 (abbreviated as NCM96), LiNi 0.80 Co 0.15 Al 0.05One or more of O2, LiFePO4, LiMnPO4 and their respective modified materials.
[0073] The modified materials for the above-mentioned positive electrode active materials can be doped and / or surface coated.
[0074] During the charging and discharging process, solid-state battery cells undergo Li insertion / extraction and consumption, resulting in varying Li molar content at different discharge states. In the examples of positive electrode active materials described in this disclosure, the Li molar content changes after charge-discharge cycles when these materials are used in solid-state battery cells. Furthermore, the O molar content listed in the examples of positive electrode active materials in this disclosure is only a theoretical value; lattice oxygen release causes changes in the O molar content, and the actual O molar content will also fluctuate.
[0075] In some embodiments, the positive electrode film layer further includes a positive electrode conductive agent.
[0076] Optionally, the positive electrode conductive agent may be one or more of the following, including but not limited to superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes (CNTs), graphene, carbon nanofibers, and vapor-grown carbon fibers (VGCF).
[0077] In some embodiments, the positive electrode film layer further includes a positive electrode binder.
[0078] Optionally, the positive electrode binder may include, but is not limited to, one or more of the following: polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene-propylene terpolymer, ethylene-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, styrene-butadiene rubber (SBR), water-soluble unsaturated resin SR-1B, methyl vinyl silicone rubber, nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), thermoplastic styrene-butadiene rubber (SBS), isoprene rubber, butadiene rubber (BR), ethyl cellulose, fluororubber, and acrylate rubber.
[0079] [negative electrode] In some embodiments, the negative electrode may include one or more of lithium, lithium alloy, natural graphite, artificial graphite, mesophase micro carbon spheres, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, and metal oxides.
[0080] In some embodiments, the negative electrode can be a metal sheet, such as a lithium sheet or a lithium alloy sheet.
[0081] Optionally, other elements in the lithium alloy sheet may include, but are not limited to, one or more of In, Mg, Al, Zn, Sn, Ag, Au, Ga, Pt, and Fe.
[0082] Alternatively, the lithium alloy sheet may include, but is not limited to, In-Li alloy sheet, Li-Mg alloy sheet, Li-Al alloy sheet, Li-Zn alloy sheet, Li-Ag alloy sheet, etc.
[0083] In some embodiments, the negative electrode may include a negative electrode current collector and a lithium-based metal layer located on at least one surface of the negative electrode current collector. The lithium-based metal layer may be metallic lithium or a lithium alloy. The negative electrode current collector has two surfaces opposite each other in its thickness direction, and the lithium-based metal layer is disposed on either or both of the two opposite surfaces of the negative electrode current collector.
[0084] Optionally, other elements in the lithium alloy may include, but are not limited to, one or more of In, Mg, Al, Zn, Sn, Ag, Au, Ga, Pt, and Fe.
[0085] Alternatively, the lithium alloy may include, but is not limited to, In-Li alloy, Li-Mg alloy, Li-Al alloy, Li-Zn alloy, Li-Ag alloy, etc.
[0086] In some embodiments, the negative electrode may include a negative electrode current collector and a negative electrode active material layer located on at least one side of the negative electrode current collector, the negative electrode active material layer comprising a negative electrode active material. The negative electrode current collector has two surfaces opposite to each other in its thickness direction, and the negative electrode active material layer is disposed on either or both of the two opposite surfaces of the negative electrode current collector.
[0087] Optionally, the negative electrode active material may include, but is not limited to, one or more of the following: natural graphite, artificial graphite, mesophase micro carbon spheres, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, and metal oxides.
[0088] Optionally, the silicon-based material may include, but is not limited to, one or more of elemental silicon, silicon oxide, silicon-carbon composites, silicon-nitrogen composites, and silicon alloys. Optionally, the tin-based material may include, but is not limited to, one or more of elemental tin, tin oxide, and tin alloys. Optionally, the metal oxide may include, but is not limited to, one or more of TiO2, MoO2, In2O3, Al2O3, Cu2O, VO2, Ga2O3, Sb2O5, and Bi2O5.
[0089] In some embodiments, the negative electrode active material layer further includes a negative electrode binder.
[0090] Optionally, the negative electrode binder may include, but is not limited to, one or more of the following: styrene-butadiene rubber (SBR), water-soluble unsaturated resin SR-1B, polyacrylic acid, polymethacrylic acid, sodium polyacrylate, polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), carboxymethyl chitosan (CMCS), methyl vinyl silicone rubber, nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), thermoplastic styrene-butadiene rubber (SBS), isoprene rubber, cis-butadiene rubber (BR), ethyl cellulose, fluororubber, and acrylate rubber.
[0091] In some embodiments, the negative electrode active material layer may or may not include a negative electrode conductive agent.
[0092] Optionally, the negative electrode conductive agent may be one or more of the following, including but not limited to superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes (CNTs), graphene, carbon nanofibers, and vapor-grown carbon fibers (VGCF).
[0093] In some embodiments, the negative electrode current collector may be a metal foil or a composite current collector. The metal foil may be a pure metal, an alloy, or a surface-treated metal, such as, but not limited to, stainless steel foil, copper foil, and nickel foil. The composite current collector may include a polymer substrate and a metal layer formed on at least one surface of the polymer substrate. As an example, the metal layer may include, but is not limited to, one or more of copper, copper alloys, nickel, nickel alloys, titanium, titanium alloys, silver, and silver alloys. As an example, the polymer substrate may include, but is not limited to, one or more of polypropylene, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene, and polyethylene.
[0094] The negative electrode can be prepared by either a dry process or a wet process.
[0095] [Electrolyte layer] In some embodiments, the electrolyte layer comprises a solid electrolyte.
[0096] Optionally, the solid electrolyte may include one or more of sulfide solid electrolytes, halide solid electrolytes, and oxide solid electrolytes.
[0097] Optionally, the sulfide solid electrolyte may include Li 6+m+l P 1-m M m S 5-n+l N n Y 1-l The material, with the molecular formula Li 10±δ Ge 1-g G g P 2-q Qq S 12-w W w Materials, Li 4-v Ge 1-v P v One or more of the following materials: S4, Li2S-P2S5, Li2S-SiS2, Li2S-MeS-P2S5, and LiGeGaS; 0 ≤ m < 1, 0 ≤ n < 1, -1 < l < 1; M includes one or more elements of Ge, Si, Sn, Al, Zr, and Sb; N includes one or more elements of O, Se, and Te; Y includes one or more elements of Cl, Br, and I; 0 ≤ δ < 1, 0 ≤ g ≤ 1, 0 ≤ q ≤ 2, 0 ≤ w < 1; G includes one or two elements of Si and Sn; Q includes Sb; W includes one or more elements of O, Se, Te, Cl, Br, and I; 0 < v < 1; Me includes one or more elements of Si, Ge, Sn, and Al.
[0098] As an example, sulfide electrolytes may include Li6PS5Cl, Li6PS5Br, Li6PS5I, and Li6PS5Cl. 0.5 Br 0.5 Li 5.5 PS 4.5 Cl 1.5 Li 5.5 PS 4.5 Br 1.5 Li 10 GeP2S 12 Li3PS4, Li7P3S 11 Li 3.25 Ge 0.25 P 0.75 S4, Li6GaGe2S 10 One or more of them.
[0099] Optionally, the sulfide electrolyte may include Li6PS5Cl, Li6PS5Br, Li6PS5I, or Li6PS5Cl. 0.5 Br 0.5 Li 5.5 PS 4.5 Cl 1.5 Li 5.5 PS 4.5 Br 1.5 Li 10 GeP2S 12 One or more of them.
[0100] Optionally, the halide solid electrolyte may be one or more of Li3YCl6, Li3YBr6, Li3ErCl6, Li3InCl6, and Li3InBr6, including but not limited to.
[0101] Optionally, the oxide solid electrolyte may include one or more of the following: NASICON type solid electrolyte, LISICON type solid electrolyte, perovskite type solid electrolyte, and garnet type solid electrolyte.
[0102] As an example, oxide solid electrolytes may include, but are not limited to, Li5La3Ti2O 12 Li7La3Zr2O 12 Li4Ti5O 12 Li 14 Zn(GeO4)4, LiTi2(PO4)3, Li 1+x Al x Ti 2-x (PO4)3, Li 1+y Al y Ge 2-y One or more of (PO4)3, 0 < x < 2, 0 < y < 2.
[0103] In some embodiments, the electrolyte layer may or may not include a binder, depending on the manufacturing process of the solid-state battery cell. Optionally, the binder may include, but is not limited to, one or more of the following: polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene-propylene terpolymer, ethylene-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, styrene-butadiene rubber (SBR), water-soluble unsaturated resin SR-1B, methyl vinyl silicone rubber, nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), thermoplastic styrene-butadiene rubber (SBS), isoprene rubber, butadiene rubber (BR), ethyl cellulose, fluororubber, and acrylate rubber.
[0104] The electrolyte layer can be prepared by a dry process or a wet process.
[0105] In some embodiments, the solid-state battery cell may further include an outer packaging for accommodating the electrode assembly formed by assembling the negative electrode, electrolyte layer, and positive electrode. The outer packaging may be a rigid shell, such as a hard plastic shell, aluminum shell, or steel shell. The outer packaging may also be a flexible package, such as a pouch. The material of the flexible package may be plastic, such as one or more of aluminum-plastic film, polypropylene, polybutylene terephthalate (PBT), and polybutylene succinate (PBS).
[0106] [Preparation methods for solid-state battery cells] The preparation methods of solid-state battery cells are well known. For example, the assembly methods of solid-state battery cells include, but are not limited to, hard-case batteries and soft-pack batteries.
[0107] Example The following embodiments describe the disclosure of this application in more detail. These embodiments are merely illustrative, as various modifications and variations will be apparent to those skilled in the art within the scope of the disclosure of this application. Unless otherwise stated, all parts, percentages, and ratios reported in the following embodiments are based on mass, and all reagents used in the embodiments are commercially available or synthesized by conventional methods and can be used directly without further processing, and the instruments used in the embodiments are commercially available.
[0108] Example 1 Preparation of positive electrode The second active material is lithium-rich manganese-based Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O2 (LRMO), the first active material LiNbOCl4, and the conductive agent carbon nanotubes (CNTs) were mixed in a mass ratio of 45:50:5 to obtain the positive electrode powder.
[0109] Preparation of electrolyte layer The sulfide electrolyte Li6PS5Cl and the halide electrolyte Li3YCl6, with a mass ratio of 1:1, were used as electrolyte layer powders.
[0110] Preparation of negative electrode Lithium-indium alloy is used as the negative electrode.
[0111] Preparation of solid-state battery cells using molds Solid-state battery cells are assembled using a 10 mm diameter solid-state battery cell mold: the above-mentioned electrolyte layer powder is added to the solid-state battery cell mold and cold-pressed into a sheet under a pressure of 2 t to obtain the electrolyte layer; then the prepared positive electrode powder is evenly spread on the other side of the electrolyte layer and compacted under a pressure of 5 t; finally, a layer of lithium indium alloy is attached to the negative electrode side and pressed together in the mold under a pressure of 0.5 t to obtain the solid-state battery cell.
[0112] Comparative Example 1 The experimental steps are basically the same as in Example 1, except that the voltage platforms of the first active material and the second active material are not matched in the preparation of the positive electrode, specifically because the types of the first active material are different.
[0113] Preparation of positive electrode The second active material, lithium-rich manganese-based cathode Li 1.2Mn 0.54 Ni 0.13 Co 0.13 O2 (LRMO), the first active material Li3YCl6, and the conductive agent carbon nanotubes (CNTs) were mixed in a mass ratio of 45:50:5 to obtain the positive electrode powder.
[0114] Performance testing 1. Cyclic performance testing of solid-state battery cells At 25°C, the solid-state battery cells were first charged to 3.0 V to 5.0 V at a current density of 0.1 C. vs. Li / Li + (Based on the redox platform of the positive electrode active material), let stand for 1 min, then discharge to 2.0 V at a current density of 0.1 C. vs. Li / Li + The discharge capacity at this point is denoted as C1. The solid-state battery cell is cycled 100 times at a current density of 0.1 C, and the discharge capacity at this point is denoted as C2. The capacity retention rate of the solid-state battery cell after 100 cycles at a current density of 0.1 C = C2 / C1 × 100%.
[0115] 2. Test method for redox voltage plateau of cyclic voltammetry curves of positive electrode active materials: The above-mentioned positive electrode layer was assembled into a test battery with lithium metal as the counter electrode, and then cyclic voltammetry (CV) was performed. The scan rate was 0.10 mV / s, the voltage range was 2 V–5 V, and 3 scans were performed. The voltage corresponding to the peak point of the first cyclic voltammetry curve was taken as the oxidation initiation potential.
[0116] Table 1 As shown in the table above, when the first and second active materials of this application are used in combination, the solid-state battery cell can have high capacity and good cycle performance.
[0117] Examples 1-1 to Examples 1-3 The experimental steps are basically the same as in Example 1, except that the types of the first and second active materials are different in the preparation of the positive electrode.
[0118] Table 2 As shown in the table above, different types of the first and second active materials can affect the voltage matching between the first and second active materials, thereby changing the capacity and cycle performance of the solid-state battery cell.
[0119] Examples 2-1 to 2-3 The experimental steps are basically the same as in Example 1, except that the mass ratio of the first active material and the second active material is different in the preparation of the positive electrode.
[0120] Table 3 As shown in the table above, different mass ratios of the first and second active materials can affect ionic conductivity and discharge capacity, thereby altering the cycle performance and energy density of solid-state battery cells.
[0121] The above description is merely a specific implementation of this application. Those skilled in the art will clearly understand that, for the sake of convenience and brevity, the specific working processes of the systems, modules, and units described above can be referred to the corresponding processes in the foregoing method embodiments, and will not be repeated here. It should be understood that the protection scope of this application is not limited thereto. Any person skilled in the art can easily conceive of various equivalent modifications or substitutions within the technical scope disclosed in this application, and these modifications or substitutions should all be covered within the protection scope of this application.
Claims
1. A solid-state battery cell, comprising a positive electrode, a negative electrode, and an electrolyte layer, wherein the electrolyte layer is located between the negative electrode and the positive electrode, characterized in that, At least one of the positive electrode and the negative electrode includes an electrode current collector and an electrode film layer located on at least one side of the electrode current collector. The electrode film layer includes an electrode active material, which includes a first active material and a second active material. The charge / discharge voltage range of the first active material and the charge / discharge voltage range of the second active material overlap. The first active material includes one or more compounds with the structure Li-MX and Li-MXA, wherein M includes one of Fe, Mo, W, Nb, Ta, Zr, V, In, Sc, Y, Ga, and Ln; X includes one or more of F, Cl, Br, and I; and A includes O, N, S, and PO4. 3 CO3 2 SiO4 4 SO4 2 C2O4 2 BO2 ClO4 P2O7 4 BF4 and OH One or more of them.
2. The solid-state battery cell according to claim 1, characterized in that, The overlap between the charge / discharge voltage range of the first active material and the charge / discharge voltage range of the second active material is greater than 50%.
3. The solid-state battery cell according to claim 1, characterized in that, The charge / discharge voltage range of the first active material is 0.1–4.2 V; and / or, The charge / discharge voltage range of the second active material is 0–5 V.
4. The solid-state battery cell according to claim 3, characterized in that, When the electrode active material is a positive electrode active material, the charge / discharge voltage range of the first active material is 0.1–4.2 V, and the charge / discharge voltage range of the second active material is 2–5 V; and / or, When the electrode active material is a negative electrode active material, the charge / discharge voltage range of the first active material is 0.1–4.2 V, and the charge / discharge voltage range of the second active material is 0–2.5 V.
5. The solid-state battery cell according to claim 1, characterized in that, The mass ratio of the first active material to the second active material in the electrode film is 5:95–50:
50.
6. The solid-state battery cell according to claim 1, characterized in that, The first active material includes Li2FeCl4 and Li 1.3 Fe 1.2 One or more of the following: Cl4, Li3VCl6, Li3TiCl6, Li2ZrCl6, Li3InCl6, LiTaCl6, Li2ZrOCl4, LiNbOCl4, and Li2CO3-TaCl5.
7. The solid-state battery cell according to claim 1, characterized in that, When the electrode active material is a positive electrode active material, the second active material includes one or more of lithium transition metal oxides and their modified materials, lithium-containing phosphates and their modified materials, and conversion-type positive electrodes. Optionally, the lithium transition metal oxide includes one or more of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, and lithium-rich manganese-based materials. The lithium-containing phosphate includes one or more of lithium iron phosphate, lithium iron phosphate and carbon composite materials, lithium manganese phosphate, lithium manganese phosphate and carbon composite materials, lithium manganese iron phosphate, and lithium manganese iron phosphate and carbon composite materials. The conversion-type positive electrode includes one or more of sulfur, sulfur and carbon composite materials, selenium, selenium and carbon composite materials, iodine, iodine and carbon composite materials, metal sulfides, metal selenides, and metal halides.
8. The solid-state battery cell according to claim 1, characterized in that, When the electrode active material is a negative electrode active material, the second active material includes one or more of lithium, lithium alloy, natural graphite, artificial graphite, mesophase micro carbon spheres, soft carbon, hard carbon, silicon-based materials, tin-based materials, phosphorus-based materials, lithium titanate, and metal oxides.
9. The solid-state battery cell according to claim 7, characterized in that, When the element M in the first active material includes one or more of Fe, Mo, W, Nb, Ta, V, In, Yb, Eu, and Ga, the second active material includes a lithium transition metal oxide; and / or, When the element M in the first active material includes one or more of Fe, Mo, W, Nb, Ta, V, In, Yb, Eu, and Ga, the second active material includes a lithium phosphate; and / or, When the M element in the first active material includes one or more of Zr, Yb, Ta, Ga, and W, the second active material includes lithium titanate; and / or, When the M element in the first active material includes one or more of Zr, Yb, Ta, Ga, and W, the second active material includes sulfur.
10. The solid-state battery cell according to claim 8, characterized in that, When the M element in the first active material includes one or more of Y, Sc, and Ln, the second active material includes one or more of lithium alloy, natural graphite, artificial graphite, mesophase micro carbon spheres, soft carbon, hard carbon, silicon-based materials, tin-based materials, and phosphorus-based materials.
11. A battery device, characterized in that, It includes any of the solid-state battery cells according to any one of claims 1-10.
12. An electrical appliance, characterized in that, Includes the solid-state battery cell according to any one of claims 1-10 or the battery device according to claim 11.