Positive electrode active material, positive electrode sheet, solid-state battery cell, battery apparatus, and electric apparatus

Abstract

The present disclosure provides a positive electrode active material, a positive electrode sheet, a solid-state battery cell, a battery apparatus, and an electric apparatus. The positive electrode sheet comprises the positive electrode active material and a sulfide solid-state electrolyte material. The positive electrode active material comprises a matrix material and a coating material located on at least a part of the surface of the matrix material. The matrix material includes a lithium-rich manganese-based material, and the coating material includes one or more of indium halide, indium sulfide In2S3, indium selenide In2Se3, and indium telluride In2Te3. The positive electrode sheet is applied to the solid-state battery cell, which can reduce the capacity degradation rate of the solid-state battery cell and improve the cycle performance of the solid-state battery cell.

Description

Positive electrode active material, positive electrode sheet, solid-state battery cell, battery device, power utilization device

[0001] Cross Reference to Related Applications

[0002] This application claims priority to Chinese Patent Application No. 202411352692.6, filed on September 26, 2024, entitled “Positive electrode active material, positive electrode sheet, solid-state battery cell, battery device, power utilization device”, the entire contents of which are incorporated herein by reference. TECHNICAL FIELD

[0003] The present disclosure relates to a positive electrode active material, a positive electrode sheet, a solid-state battery cell, a battery device, and a power utilization device. BACKGROUND

[0004] Compared with battery cells using liquid electrolyte, solid-state battery cells use solid-state electrolyte material, and are less likely to cause combustion and explosion, thus having higher reliability. However, solid-state battery cells have the problem of fast capacity decay. SUMMARY

[0005] The present disclosure provides a positive electrode active material, a positive electrode sheet, a solid-state battery cell, a battery device, and a power utilization device. The positive electrode sheet is applied to the solid-state battery cell, and can reduce the capacity decay rate of the solid-state battery cell and improve the cycle performance of the solid-state battery cell.

[0006] In a first aspect, the present disclosure provides a positive electrode sheet, the positive electrode sheet comprising a positive electrode active material and a sulfide solid-state electrolyte material, the positive electrode active material comprising a base material and a coating material on at least part of a surface of the base material, the base material comprising a lithium-rich manganese-based material, and the coating material comprising one or more of indium halide, indium sulfide In2S3, indium selenide In2Se3, and indium telluride In2Te3.

[0007] The coating material on the surface of the lithium-rich manganese-based material of the present disclosure comprises one or more of indium halide, indium sulfide In2S3, indium selenide In2Se3, and indium telluride In2Te3. These coating materials have good stability with the lithium-rich manganese-based material, and are coated on the surface of the lithium-rich manganese-based material, which can reduce the interfacial side reactions between the lithium-rich manganese-based material and the sulfide solid-state electrolyte material.

[0008] The coating material of the present disclosure also has high ionic conductivity, and coating on the surface of the lithium-rich manganese-based material can also improve the ion conduction on the surface of the lithium-rich manganese-based material, thereby improving the utilization rate of anion redox and the actual discharge capacity of the lithium-rich manganese-based material.

[0009] The coating material of the present disclosure contains indium ions, and there is a certain coupling relationship between the oxygen ion redox of the lithium-rich manganese-based material and the redox of the indium ions. The lithium-rich manganese-based material undergoes an oxidation process from O 2- to O2 2- during charging, thereby providing high capacity, and in this process, O2 2- can form an In-O bond with the indium ions in the coating material, thereby reducing the oxygen release of the lithium-rich manganese-based material; the In-O bond can be reduced to an In-X bond (X represents halogen), an In-S bond, an In-Se bond, or an In-Te bond during the discharging process, thereby also continuing to play a role in reducing oxygen release in the subsequent cyclic charging and discharging process.

[0010] Therefore, the coating material of the present disclosure can improve the cycle stability of the lithium-rich manganese-based material, reduce the side reaction between the lithium-rich manganese-based material and the sulfide solid electrolyte material, and reduce oxygen release. The positive electrode sheet of the present disclosure applied to a solid-state battery monomer can reduce the capacity decay rate of the solid-state battery monomer and improve the cycle performance of the solid-state battery monomer.

[0011] In some embodiments, the mass fraction of the coating material is 0.1%-5% based on the total mass of the positive electrode active material being 100%.

[0012] The mass fraction of the coating material in the above range can make the positive electrode active material have high ionic conductivity, high capacity, and low oxygen release.

[0013] In some embodiments, the thickness of the coating material is 0.5 nm-50 nm.

[0014] The thickness of the coating material in the above range can make the positive electrode active material have high ionic conductivity, high capacity, and low oxygen release.

[0015] In some embodiments, the coating material includes a first coating material and a second coating material, the first coating material is located on at least part of the surface of the base material, the second coating material is located on at least part of the surface of the first coating material, the first coating material includes one or more of indium halide, indium sulfide In2S3, indium selenide In2Se3, and indium telluride In2Te3, and the second coating material includes an indium-containing halide solid electrolyte material.

[0016] By having the coating material include the first coating material and the second coating material, the first coating material of the inner layer can play a role in reducing oxygen release, and the indium-containing halide solid electrolyte material of the outer layer can play a role in improving interface ion conduction, thereby the cycle performance and discharge capacity of the base material in the solid-state battery cell can be better improved. In addition, the first coating material of the inner layer can also better maintain the crystal structure stability of the indium-containing halide solid electrolyte material of the outer layer, so that the positive active material can maintain high ionic conductivity during the cycle process.

[0017] Optionally, the mass fraction of the coating material is 0.1%-5% based on 100% of the total mass of the positive active material.

[0018] The mass fraction of the coating material in the above range can make the positive active material have high ionic conductivity, high capacity play, and low oxygen release.

[0019] Optionally, the thickness of the coating material is 0.5nm-50nm.

[0020] The thickness of the coating material in the above range can make the positive active material have high ionic conductivity, high capacity play, and low oxygen release.

[0021] In some embodiments, the second coating material includes one or more of Li3InCl6, Li2In a Sc (2-a) / 3 Cl4, Li3Y 1-b In b Cl6, Li 3- c In 1-c Zr c Cl6, 0

[0022] In some embodiments, the mass ratio of the first coating material to the second coating material is 0.02:1 to 50:1.

[0023] By having the mass ratio of the first coating material to the second coating material in the above range, the cycle performance and discharge capacity of the solid-state battery cell can be further improved.

[0024] In some embodiments, the ratio of the thickness of the coating layer formed by the first coating material to the thickness of the coating layer formed by the second coating material is 0.01:1 to 100:1.

[0025] By having the ratio of the thickness of the coating layer formed by the first coating material to the thickness of the coating layer formed by the second coating material in the above range, the cycle performance and discharge capacity of the solid-state battery cell can be further improved.

[0026] In some embodiments, the coating material is located on 90% to 100% of the surface of the base material.

[0027] In some embodiments, the mass ratio of the positive electrode active material to the sulfide solid electrolyte material is 99:1 to 50:50.

[0028] The mass ratio of the positive electrode active material to the sulfide solid electrolyte material in the above range can enable the solid-state battery cell to have high energy density, high ion transport characteristics, and good cycle performance.

[0029] In some embodiments, the average particle size of the positive electrode active material is 0.5 μm-10 μm.

[0030] In some embodiments, the average particle size of the sulfide solid electrolyte material is 50 nm-1000 nm.

[0031] The average particle size of the sulfide solid electrolyte material in the above range can improve the contact between the positive electrode active material and the sulfide solid electrolyte material in the positive electrode sheet, and improve the ion conductivity of the positive electrode as a whole.

[0032] In some embodiments, the positive electrode sheet further comprises a positive electrode conductive agent and / or a positive electrode binder.

[0033] In some embodiments, the positive electrode sheet further comprises a positive electrode current collector, and the positive electrode active material and the sulfide solid electrolyte material are located on at least one surface of the positive electrode current collector.

[0034] In a second aspect, the present disclosure provides a solid-state battery cell, comprising a negative electrode sheet, an electrolyte sheet, and the positive electrode sheet of the first aspect, the electrolyte sheet being located between the negative electrode sheet and the positive electrode sheet.

[0035] In some embodiments, the negative electrode sheet comprises one or more of lithium, lithium alloy, natural graphite, artificial graphite, mesophase carbon microbeads, soft carbon, hard carbon, silicon-based material, tin-based material, lithium titanate, and metal oxide.

[0036] In some embodiments, the electrolyte sheet comprises a solid electrolyte material.

[0037] In a third aspect, the present disclosure provides a battery device comprising a plurality of the solid-state battery cells of the second aspect.

[0038] In a fourth aspect, the present disclosure provides an electrically powered device comprising the solid-state battery cell of the second aspect or the battery device of the third aspect.

[0039] In some embodiments, the coating material includes a first coating material and a second coating material, the first coating material is located on at least part of the surface of the base material, and the second coating material is located on at least part of the surface of the first coating material, the first coating material includes one or more of indium halide, indium sulfide In2S3, indium selenide In2Se3, and indium telluride In2Te3, and the second coating material includes an indium-containing halide solid electrolyte material.

[0040] In some embodiments, the coating material includes a first coating material and a second coating material, the first coating material is located on at least part of the surface of the base material, and the second coating material is located on at least part of the surface of the first coating material, the first coating material includes one or more of indium halide, indium sulfide In2S3, indium selenide In2Se3, and indium telluride In2Te3, and the second coating material includes an indium-containing halide solid electrolyte material.

[0041] In some embodiments, the second coating material includes Li3InCl6, Li2In a Sc (2-a) / 3 Cl4, Li3Y 1-b In b Cl6, Li 3- c In 1-c Zr c Cl6, 0 BRIEF DESCRIPTION OF DRAWINGS

[0042] In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the drawings needed to be used in the embodiments of the present disclosure will be briefly introduced below. Obviously, the drawings described below are only some of the embodiments of the present disclosure, and other drawings can also be obtained according to the drawings without creative labor.

[0043] FIG. 1 shows a schematic diagram of a solid-state battery cell according to some embodiments of the present disclosure.

[0044] FIG. 2 shows a schematic diagram of an electrical device according to some embodiments of the present disclosure.

[0045] In the drawings, the drawings are not necessarily drawn according to the actual proportions. DETAILED DESCRIPTION

[0046] Hereinafter, specific embodiments of the positive electrode active material, the positive electrode sheet, the solid-state battery cell, the battery device, and the power-consuming device of the present disclosure will be described in detail with appropriate reference to the accompanying drawings. However, there will be cases where unnecessary detailed description is omitted. For example, there will be cases where detailed description of matters known well, repeated description of substantially identical structures are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided so that those skilled in the art can fully understand the present disclosure, and are not intended to limit the subject matter recited in the claims.

[0047] The ranges disclosed by the present disclosure are defined in the form of lower and upper limits, and a given range is defined by selecting one lower limit and one upper limit, and the selected lower limit and upper limit define the boundaries of a particular range. The ranges defined in this way can be inclusive or exclusive of the end values, and can be arbitrarily combined, i.e., any lower limit can be combined with any upper limit to form a range. For example, if the ranges 60-120 and 80-110 are listed for a particular parameter, it is understood that the ranges 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In the present disclosure, unless otherwise specified, a numerical range "a-b" represents a shorthand notation for any real combination of integers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed herein, and "0-5" is just a shorthand notation for these numerical combinations. In addition, when it is stated that a certain parameter is an integer ≥ 2, it is equivalent to disclose that the parameter is, for example, an integer 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0048] Unless otherwise specified, all embodiments and optional embodiments of the present disclosure can be combined with each other to form new technical solutions, and such technical solutions should be considered to be included in the disclosure of the present disclosure.

[0049] Unless otherwise specified, all technical features and optional technical features of the present disclosure can be combined with each other to form new technical solutions, and such technical solutions should be considered to be included in the disclosure of the present disclosure.

[0050] If not otherwise specified, all steps of the present disclosure can be performed in sequence or randomly, preferably in sequence. For example, the method comprising steps (a) and (b) means that the method can comprise steps (a) and (b) in sequence, or steps (b) and (a) in sequence. For example, the method comprising step (c) means that step (c) can be added to the method in any sequence, for example, the method can comprise steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.

[0051] If not otherwise specified, in the present disclosure, the terms "first", "second", etc. are used to distinguish different objects, rather than to describe a specific sequence or primary and secondary relationship.

[0052] In the present disclosure, the terms "a plurality of" and "a plurality of kinds" mean two or more.

[0053] In the description of the embodiments of the present disclosure, if not otherwise specified, the first feature is "on" or "under" the second feature can mean that the first and second features are in direct contact, or the first and second features are in indirect contact through an intermediate medium. Moreover, the first feature can be "above", "over" and "on" the second feature, which can mean that the first feature is directly above or obliquely above the second feature, or only means that the first feature is horizontally higher than the second feature. The first feature can be "under", "below" and "underneath" the second feature, which can mean that the first feature is directly below or obliquely below the second feature, or only means that the first feature is horizontally lower than the second feature.

[0054] Unless otherwise specified, the test temperature of each parameter mentioned in the present disclosure is 25℃.

[0055] The solid-state battery cell mentioned in the embodiments of the present disclosure can realize the function of charging and discharging independently. The solid-state battery cell can be in the shape of a cylinder, a cuboid or other shapes, which are not limited in the embodiments of the present disclosure. As shown in FIG. 1, the solid-state battery cell 5 is a cuboid structure as an example.

[0056] The battery apparatus mentioned in the embodiments of the present disclosure can comprise one or more battery cell assemblies for providing voltage and capacity. The battery cell assembly can comprise a plurality of solid-state battery cells connected in series, in parallel or in a mixed manner through a busbar component.

[0057] In some embodiments, the battery cell assembly is usually formed by arranging a plurality of solid-state battery cells.

[0058] As an example, the battery cell assembly can be a battery module. The battery module is formed by arranging and fixing a plurality of solid-state battery cells into one independent module.

[0059] In some embodiments, the battery device can be a battery pack. The battery pack includes a case and one or more battery cell assemblies. The battery cell assemblies are accommodated in the case.

[0060] As an example, the battery cell assembly can be a battery module. The battery cell assembly can be accommodated in the case by fixing the battery module in the case.

[0061] As an example, the battery cell assembly can also be accommodated in the case by directly fixing a plurality of solid-state battery cells in the case.

[0062] As an example, the case can include a first case and a second case. The first case and the second case are fastened so that an enclosed space is formed inside the case to accommodate the battery cell assembly. Here, enclosed means covered or closed, which can be sealed or unsealed. The first case can be a top cover or a bottom plate.

[0063] As an example, the case can include a top cover, a frame, and a bottom plate. The top cover and the bottom plate are respectively connected to the frame so that an enclosed space is formed inside the case to accommodate the battery cell assembly.

[0064] In some embodiments, the case can be part of the chassis structure of a vehicle. For example, part of the case can be at least part of the floor of the vehicle, or part of the case can be at least part of the cross beam and the longitudinal beam of the vehicle.

[0065] The technical solutions described in the embodiments of the present disclosure are applicable to various electric devices using solid-state battery cells and battery devices. For example, the electric devices can be, but are not limited to, mobile devices (such as mobile phones, tablet computers, notebook computers, etc.), electric vehicles (such as 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. The solid-state battery cells and the battery devices are used to store or provide electric energy.

[0066] FIG. 2 is a schematic diagram of an electric device as an example. The electric device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc.

[0067] The lithium-rich manganese-based material has the advantages of high theoretical specific capacity, high energy density, low cost, good thermal stability, etc., and thus becomes a promising next-generation positive electrode active material. Using the lithium-rich manganese-based material in a solid-state battery cell is expected to make the solid-state battery cell have high energy density and high reliability.

[0068] However, the lithium-rich manganese-based material has low ionic conductivity, slow anion redox process dynamics, and interface side reactions between the lithium-rich manganese-based material and the sulfide solid-state electrolyte material due to the difference in electrochemical potential, which results in a low actual discharge capacity of the lithium-rich manganese-based material, which is much lower than the theoretical capacity. In addition, the anion redox process of the lithium-rich manganese-based material also causes oxygen release problems, and oxygen can oxidize the sulfide solid-state electrolyte material, which also causes continuous capacity and voltage decay of the solid-state battery cell, thereby affecting the electrochemical performance of the lithium-rich manganese-based material in the solid-state battery cell and its practical application.

[0069] Currently, oxides such as Li3BO3 and Li2ZrO3 are used to coat the lithium-rich manganese-based material. These oxide coating materials can reduce the interface side reactions between the lithium-rich manganese-based material and the sulfide solid-state electrolyte material, but they cannot effectively improve the ionic conductivity of the lithium-rich manganese-based material or solve the oxygen release problem of the lithium-rich manganese-based material, which results in unsatisfactory electrochemical performance of the solid-state battery cell using the lithium-rich manganese-based material.

[0070] Based on this, the present disclosure provides a positive electrode active material and a positive electrode sheet containing the same, which is applied to a solid-state battery cell, can reduce the capacity decay rate of the solid-state battery cell, and improve the cycle performance of the solid-state battery cell.

[0071] The positive electrode sheet of the present disclosure includes a positive electrode active material and a sulfide solid-state electrolyte material.

[0072] The positive electrode active material includes a base material and a coating material on at least part of the surface of the base material. The base material includes a lithium-rich manganese-based material, and the coating material includes one or more of indium halide, indium sulfide In2S3, indium selenide In2Se3, and indium telluride In2Te3.

[0073] The actual discharge capacity of the lithium-rich manganese-based material without surface coating is very low, and there is basically no anion redox process involved, which results in poor electrochemical performance of the solid-state battery cell using the lithium-rich manganese-based material.

[0074] After coating the lithium-rich manganese-based material with oxides such as Li3BO3 and Li2ZrO3, the actual discharge capacity of the lithium-rich manganese-based material is improved to a certain extent, but the electrochemical performance of the solid-state battery cell is still not ideal.

[0075] The coating material on the surface of the lithium-rich manganese-based material of the present disclosure includes one or more of indium halide, indium sulfide In2S3, indium selenide In2Se3, and indium telluride In2Te3. These coating materials have good stability with the lithium-rich manganese-based material, and can be coated on the surface of the lithium-rich manganese-based material to reduce the interface side reactions between the lithium-rich manganese-based material and the sulfide solid electrolyte material.

[0076] The coating material of the present disclosure also has high ionic conductivity, and coating on the surface of the lithium-rich manganese-based material can also improve the ionic conduction of the surface of the lithium-rich manganese-based material, thereby improving the utilization rate of anion redox and the actual discharge capacity of the lithium-rich manganese-based material.

[0077] The coating material of the present disclosure contains indium ions, and there is a certain coupling relationship between the oxygen ion redox of the lithium-rich manganese-based material and the redox of the indium ions. When the lithium-rich manganese-based material is charged, the O 2- to O2 2- oxidation process, thereby providing high capacity. In this process, O2 2- can form In-O bonds with the indium ions in the coating material, thereby reducing the release of oxygen from the lithium-rich manganese-based material; the In-O bonds can be reduced to In-X bonds (X represents halogen), In-S bonds, In-Se bonds, or In-Te bonds in the discharge process, thereby also continuing to reduce the release of oxygen in the subsequent cyclic charging and discharging process.

[0078] Therefore, the coating material of the present disclosure can improve the cycle stability of the lithium-rich manganese-based material, reduce the side reactions between the lithium-rich manganese-based material and the sulfide solid electrolyte material, and reduce the release of oxygen. The positive electrode sheet of the present disclosure applied to a solid-state battery monomer can reduce the capacity decay rate of the solid-state battery monomer and improve the cycle performance of the solid-state battery monomer.

[0079] In some embodiments, the coating material can include one or more of InCl3, InBr3, InI3, In2S3, In2Se3, and In2Te3.

[0080] In some embodiments, the mass fraction of the coating material can be 0.1-5%, for example, can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5%, or a range consisting of any of the aforementioned values, based on the total mass of the positive electrode active material being 100%.

[0081] The mass fraction of the coating material in the above range can enable the positive electrode active material to have high ionic conductivity, high capacity release, and low oxygen release.

[0082] Alternatively, the mass fraction of the coating material can be 0.3-5%, 0.3-4.5%, 0.3-4%, 0.3-3.5%, 0.3-3%, 0.3-2.5%, 0.3-2%, 0.5-5%, 0.5-4.5%, 0.5-4%, 0.5-3.5%, 0.5-3%, 0.5-2.5%, 0.5-2%, 0.8-5%, 0.8-4.5%, 0.8-4%, 0.8-3.5%, 0.8-3%, 0.8-2.5%, 0.8-2%.

[0083] In some embodiments, the thickness of the coating material can be 0.5-50 nm, for example, can be 0.5 nm, 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, 20 nm, 21 nm, 22 nm, 23 nm, 24 nm, 25 nm, 26 nm, 27 nm, 28 nm, 29 nm, 30 nm, 32 nm, 34 nm, 36 nm, 38 nm, 40 nm, 42 nm, 44 nm, 46 nm, 48 nm, 50 nm, or a range consisting of any of the aforementioned values.

[0084] The thickness of the coating material in the above range can enable the positive electrode active material to have high ionic conductivity, high capacity release, and low oxygen release.

[0085] Optionally, the thickness of the coating material can be 0.5nm-30nm, 0.5nm-25nm, 0.5nm-20nm, 0.5nm-15nm, 0.5nm-10nm, 0.5nm-5nm, 1nm-30nm, 1nm-25nm, 1nm-20nm, 1nm-15nm, 1nm-10nm, 1nm-5nm.

[0086] In some embodiments, the coating material can include a first coating material and a second coating material, the first coating material is located on at least part of the surface of the base material, and the second coating material is located on at least part of the surface of the first coating material. The first coating material can include one or more of indium halide, indium sulfide In2S3, indium selenide In2Se3, and indium telluride In2Te3. The second coating material can include an indium-containing halide solid electrolyte material.

[0087] By having the coating material include the first coating material and the second coating material, the first coating material of the inner layer can play a role in reducing oxygen release, and the indium-containing halide solid electrolyte material of the outer layer can play a role in improving interface ion conduction, thereby better improving the cycle performance and discharge capacity of the base material in the solid-state battery cell. In addition, the first coating material of the inner layer can also better maintain the crystal structure stability of the indium-containing halide solid electrolyte material of the outer layer, so that the positive active material can maintain high ionic conductivity during the cycle process.

[0088] Optionally, the second coating material can include one or more of Li3InCl6, Li2In a Sc (2-a) / 3 Cl4, Li3Y 1-b In b Cl6, Li 3-c In 1- c Zr c Cl6, 0

[0089] Optionally, the mass fraction of the coating material can be 0.1-5%, for example, can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5%, or a range consisting of any of the aforementioned values, based on the total mass of the positive electrode active material being 100%.

[0090] The mass fraction of the coating material in the above range can make the positive electrode active material have high ionic conductivity, high capacity release, and low oxygen release.

[0091] More optionally, the mass fraction of the coating material can be 0.3-5%, 0.3-4.5%, 0.3-4%, 0.3-3.5%, 0.3-3%, 0.3-2.5%, 0.3-2%, 0.5-5%, 0.5-4.5%, 0.5-4%, 0.5-3.5%, 0.5-3%, 0.5-2.5%, 0.5-2%, 0.8-5%, 0.8-4.5%, 0.8-4%, 0.8-3.5%, 0.8-3%, 0.8-2.5%, 0.8-2%.

[0092] Optionally, the mass ratio of the first coating material to the second coating material can be 0.02:1 to 50:1, for example, can be 0.02:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 12:1, 14:1, 16:1, 18:1, 20:1, 22:1, 24:1, 26:1, 28:1, 30:1, 32:1, 34:1, 36:1, 38:1, 40:1, 42:1, 44:1, 46:1, 48:1, 50:1, or a range consisting of any of the aforementioned values.

[0093] The first coating material can reduce oxygen release, the indium-containing halide solid-state electrolyte material can improve the interface ion conduction, and the first coating material can also better maintain the stability of the crystal structure of the outer layer of the indium-containing halide solid-state electrolyte material. By making the mass ratio of the first coating material to the second coating material within the above range, the cycle performance and discharge capacity of the solid-state battery cell can be further improved.

[0094] More optionally, the mass ratio of the first coating material to the second coating material can be 0.2:1 to 50:1, 0.5:1 to 50:1, 1:1 to 50:1, 0.2:1 to 20:1, 0.5:1 to 20:1, 1:1 to 20:1, 0.2:1 to 10:1, 0.5:1 to 10:1, 1:1 to 10:1, 0.2:1 to 5:1, 0.5:1 to 5:1, 1:1 to 5:1, 0.2:1 to 3:1, 0.5:1 to 3:1, 1:1 to 3:1.

[0095] Optionally, the thickness of the coating material can be 0.5nm-50nm, for example, it can be 0.5nm, 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, 21nm, 22nm, 23nm, 24nm, 25nm, 26nm, 27nm, 28nm, 29nm, 30nm, 32nm, 34nm, 36nm, 38nm, 40nm, 42nm, 44nm, 46nm, 48nm, 50nm, or a range composed of any of the above values.

[0096] The thickness of the coating material within the above range can make the positive active material have high ion conductivity, high capacity, and low oxygen release.

[0097] More optionally, the thickness of the coating material can be 0.5nm-30nm, 0.5nm-25nm, 0.5nm-20nm, 0.5nm-15nm, 0.5nm-10nm, 0.5nm-5nm, 1nm-30nm, 1nm-25nm, 1nm-20nm, 1nm-15nm, 1nm-10nm, 1nm-5nm.

[0098] Optionally, the ratio of the thickness of the coating layer formed by the first coating material to the thickness of the coating layer formed by the second coating material can be 0.01:1 to 100:1, for example, can be 0.01:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 12:1, 14:1, 16:1, 18:1, 20:1, 22:1, 24:1, 26:1, 28:1, 30:1, 32:1, 34:1, 36:1, 38:1, 40:1, 42:1, 44:1, 46:1, 48:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, 85:1, 90:1, 95:1, 100:1, or a range composed of any of the above values.

[0099] The first coating material can play a role in reducing oxygen release, the indium-containing halide solid-state electrolyte material can play a role in improving interface ion conduction, and the first coating material can also better maintain the stability of the crystal structure of the outer layer of the indium-containing halide solid-state electrolyte material. By making the ratio of the thickness of the coating layer formed by the first coating material to the thickness of the coating layer formed by the second coating material within the above range, the cycle performance and discharge capacity of the solid-state battery cell can be further improved.

[0100] In some embodiments, the coating material can be located on 90% to 100% of the surface of the base material.

[0101] In some embodiments, the lithium-rich manganese-based material can include Li2MnO3·LiMO2, M can include one or more of Ni, Co, Mn, Cr, Fe, Al, Nb, Zr, Mo, Ta, Ru.

[0102] Optionally, the lithium-rich manganese-based material can include one or more of Li2MnO3·LiCoO2, Li2MnO3·LiNi 0.5 Mn 0.5 O2, Li2MnO3·LiNi 1-d Co d O2, Li2MnO3·LiNi e Co f Mn g O2, 0

[0103] Optionally, xLi2MnO3·LiNi e Co f Mn g O2 can include Li2MnO3·LiNi1 / 3 Co 1 / 3 Mn 1 / 3 O2, Li2MnO3·LiNi 0.5 Co 0.2 Mn 0.3 O2, Li2MnO3·LiNi 0.6 Co 0.2 Mn 0.2 O2, Li2MnO3·LiNi 0.8 Co 0.1 Mn 0.1 O2, Li2MnO3·LiNi

[0104] The solid-state battery cell will be accompanied by Li deintercalation and consumption during charging and discharging, and the molar content of Li is different when the solid-state battery cell is discharged to different states. In the enumeration of the lithium-rich manganese-based material in the present disclosure, the molar content of Li is the initial state of the material, i.e., the state before feeding. The lithium-rich manganese-based material is applied to the solid-state battery cell, and after charging and discharging cycles, the molar content of Li will change. In the enumeration of the lithium-rich manganese-based material in the present disclosure, the molar content of O is only the theoretical state value, and the release of oxygen from the lattice will cause the molar content of O to change, and the actual molar content of O will also appear to float.

[0105] In some embodiments, the average particle size of the positive active material can be 0.5-10 μm, for example, can be 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, or a range consisting of any of the above values.

[0106] In some embodiments, the sulfide solid-state electrolyte material can include, but is not limited to, one or more of argyrodite type, LGPS type, lithium sulfide phosphorus pentasulfide composite type sulfide solid-state electrolyte material.

[0107] Optionally, the argyrodite type sulfide solid-state electrolyte material can include a material with a chemical formula of Li 6±s P 1-j A j S 5±s-t B t X 1±s 0≤j<1, 0≤t<1, 0≤s<1, A includes one or more elements of Ge, Si, Sn and Sb, B includes one or more elements of O, Se and Te, and X includes one or more elements of Cl, Br, I and F.

[0108] Optionally, the LGPS type sulfide solid-state electrolyte material can include a material with a chemical formula of Li 10±δ5 Ge 1-g G g P 2-q Qq S 12- w W w of the material, 0≤δ5<1, 0≤g≤1, 0≤q≤2, 0≤w<1, G comprises one or both of Si and Sn, Q comprises Sb, and W comprises one or more of O, Se, Te, Cl, Br, I, and F.

[0109] Optionally, the lithium sulfide pentasulfide complex compound sulfide solid-state electrolyte material can include a chemical formula of (100-u-v)Li2S·uP2S5·vM m N n of the material, 0<u<100, 0≤v<100, 0≤u+v<100, 0≤m<4, 0≤n<6, M comprises one or more of Li, B, Ge, Si, Sn, and Sb, and N comprises one or more of S, Se, Te, O, Cl, Br, I, and F.

[0110] In some embodiments, as an example, the sulfide solid-state electrolyte material can include one or more of Li6PS5Cl, Li6PS5Br, Li 10 GeP2S 12 , Li3PS4, Li7P3S 11 .

[0111] In some embodiments, the average particle size of the sulfide solid-state electrolyte material can be 50nm-1000nm, for example, can be 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm, 800nm, 850nm, 900nm, 950nm, 1000nm, or a range consisting of any of the foregoing values.

[0112] The average particle size of the sulfide solid-state electrolyte material in the above range can improve the contact between the positive electrode active material and the sulfide solid-state electrolyte material in the positive electrode sheet, and improve the ionic conductivity of the positive electrode as a whole.

[0113] In some embodiments, the mass ratio of the positive active material to the sulfide solid electrolyte material can be 99:1 to 50:50, for example, can be 99:1, 98:2, 97:3, 96:4, 95:5, 94:6, 93:7, 92:8, 91:9, 90:10, 89:11, 88:12, 87:13, 86:14, 85:15, 84:16, 83:17, 82:18, 81:19, 80:20, 79:21, 78:22, 77:23, 76:24, 75:25, 74:26, 73:27, 72:28, 71:29, 70:30, 69:31, 68:32, 67:33, 66:34, 65:35, 64:36, 63:37, 62:38, 61:39, 60:40, 59:41, 58:42, 57:43, 56:44, 55:45, 54:46, 53:47, 52:48, 51:49, 50:50, or a range consisting of any of the above values.

[0114] The mass ratio of the positive active material to the sulfide solid electrolyte material in the above range can enable the solid-state battery cell to have high energy density, high ion transport characteristics, and good cycle performance.

[0115] Optionally, the mass ratio of the positive active material to the sulfide solid electrolyte material can be 95:5 to 70:30, 90:10 to 70:30, 85:15 to 70:30, 95:5 to 72:28, 90:10 to 72:28, 85:15 to 72:28.

[0116] In some embodiments, the positive electrode sheet includes a positive electrode current collector, and the positive active material and the sulfide solid electrolyte material are located on at least one surface of the positive electrode current collector.

[0117] In some embodiments, the positive electrode current collector can be a metal foil or a composite current collector. As a metal foil, pure metals, alloys, surface-treated metals can be used, for example, can include but are not limited to stainless steel foil, carbon-coated aluminum foil, aluminum foil, nickel foil, titanium foil. The composite current collector can include a polymer material base layer and a metal material layer formed on at least one surface of the polymer material base layer. As an example, the metal material can include but is not limited to one or more of aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver, and silver alloy. As an example, the polymer material base layer can include but is not limited to one or more of polypropylene, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), and polyethylene.

[0118] In some embodiments, the positive electrode sheet can not need to be additionally provided with a positive electrode current collector, for example, the stainless steel sheet of a die battery can be directly used as a positive electrode current collector.

[0119] In some embodiments, the positive electrode sheet can further comprise a positive electrode conductive agent, which can include, but is not limited to, one or more of conductive graphite (such as KS-6, SFG-6), super conductive carbon, acetylene black, carbon black (such as SP), ketjen black (such as ECP), carbon dots, carbon nanotubes, graphene, carbon nanofibers, and vapor grown carbon fiber (VGCF).

[0120] In some embodiments, the positive electrode sheet can further comprise a positive electrode binder, or can not comprise a positive electrode binder, which can be adjusted according to the composition of the positive electrode and the preparation process of the solid-state battery cell. Optionally, the positive electrode binder can include, but is not limited to, one or more of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, fluorine-containing acrylate resin, water-soluble unsaturated resin SR-1B, methyl vinyl silicone rubber, nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), styrene butadiene rubber (SBR), thermoplastic styrene butadiene rubber (SBS), isoprene rubber, butadiene rubber (BR), ethyl cellulose, polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA), carboxymethyl chitosan (CMCS), fluororubber, and acrylate rubber.

[0121] The positive electrode sheet can be prepared by a dry process or by a wet process.

[0122] The average particle size of the particles can be tested according to the following method: using a scanning electron microscope, referring to JY / T010-1996, obtaining a SEM image of the positive electrode sheet, randomly selecting a test sample with a length x width of 50 mm x 100 mm on the positive electrode sheet, randomly selecting multiple test regions (for example, 5) in the test sample, and reading the particle size of each particle in each test region under a certain magnification (for example, more than 500 times); counting the number and particle size values of the particles in each test region, taking the arithmetic mean of the particle sizes of all particles in each test region as the average particle size of the particles. In order to ensure the accuracy of the test results, multiple test samples (for example, 10) can be taken for the above test, and the average value of each test sample is taken as the final test result. The test instrument can be ZEISS Sigma 300. It should be noted that when the particles are irregularly shaped, the distance between the two farthest points on the particle is taken as the particle size of the particle.

[0123] The present disclosure also provides a solid-state battery cell comprising a negative electrode sheet, an electrolyte sheet, and a positive electrode sheet provided by the present disclosure, the electrolyte sheet being located between the negative electrode sheet and the positive electrode sheet.

[0124] The solid-state battery cell of the present disclosure can include a button cell, a dielectric cell, a hard-shell cell, a soft-pack cell, etc.

[0125] [Negative electrode sheet]

[0126] The negative electrode sheet can be prepared by a dry process or by a wet process.

[0127] In some embodiments, the negative electrode sheet can include one or more of lithium, lithium alloy, natural graphite, artificial graphite, meso-phase micro carbon sphere, soft carbon, hard carbon, silicon-based material, tin-based material, lithium titanate, metal oxide.

[0128] Optionally, the mass fraction of lithium element in the lithium alloy can be above 90%.

[0129] Optionally, the other elements in the lithium alloy can include, but are not limited to, one or more of In, Mg, Al, Zn, Sn, Ag, Au, Ga, Pt, Fe.

[0130] Optionally, the lithium alloy can include, but is not limited to, InLi alloy, Li-Mg alloy, Li-Al alloy, Li-Zn alloy, Li-Fe alloy, etc.

[0131] Optionally, the silicon-based material can include, but is not limited to, one or more of elemental silicon, silicon oxide, silicon-carbon composite material, silicon-nitrogen composite, and silicon alloy material.

[0132] Optionally, the tin-based material can include, but is not limited to, one or more of elemental tin, tin oxide, and tin alloy material.

[0133] Optionally, the metal oxide can include, but is not limited to, one or more of TiO2, MoO2, In2O3, Al2O3, Cu2O, VO2, Ga2O3, Sb2O5, Bi2O5.

[0134] In some embodiments, the negative electrode sheet can be a metal sheet, such as a lithium sheet, a lithium alloy sheet, etc.

[0135] In some embodiments, the negative electrode sheet can include a negative electrode current collector and a lithium-based metal layer on at least one surface of the negative electrode current collector. The negative electrode current collector has two opposite surfaces in the thickness direction of itself, and the lithium-based metal layer is disposed on any one or both of the two opposite surfaces of the negative electrode current collector.

[0136] In some embodiments, the lithium-based metal layer can include lithium or lithium alloy.

[0137] In some embodiments, the negative electrode sheet can include a negative electrode current collector and a negative electrode film layer on at least one surface of the negative electrode current collector, the negative electrode film layer including a negative electrode active material. The negative electrode current collector has two surfaces opposite in the thickness direction of the negative electrode current collector, and the negative electrode film layer is disposed on either one or both of the two opposite surfaces of the negative electrode current collector.

[0138] In some embodiments, the negative electrode active material can include, but is not limited to, one or more of natural graphite, artificial graphite, mesocarbon microbeads, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, metal oxides.

[0139] In some embodiments, the negative electrode film layer further includes a negative electrode binder, which can include, but is not limited to, one or more of styrene butadiene rubber (SBR), water-soluble unsaturated resin SR-1B, polyacrylic acid, polymethacrylic acid, sodium polyacrylate, polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA) and carboxymethyl chitosan (CMCS), methyl vinyl silicone rubber, nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), thermoplastic styrene butadiene rubber (SBS), isoprene rubber, butadiene rubber (BR), ethyl cellulose, fluororubber, acrylate rubber.

[0140] In some embodiments, the negative electrode film layer can further include a negative electrode conductive agent, or can not include a negative electrode conductive agent.

[0141] Optionally, the negative electrode conductive agent can include, but is not limited to, one or more of conductive graphite (such as KS-6, SFG-6), superconducting carbon, acetylene black, carbon black (such as SP), ketjen black (such as ECP), carbon dots, carbon nanotubes, graphene, carbon nanofibers, vapor grown carbon fiber (VGCF).

[0142] In some embodiments, the negative electrode film layer can further include a solid-state electrolyte material, or can not include a solid-state electrolyte material. Optionally, the solid-state electrolyte material can include, but is not limited to, one or more of sulfide solid-state electrolyte material, halide solid-state electrolyte material, oxide solid-state electrolyte material.

[0143] The types of sulfide solid-state electrolyte material can refer to the sulfide solid-state electrolyte material in the positive electrode sheet described above, which will not be repeated here.

[0144] Optionally, the halide solid-state electrolyte material can include one or more of Li3YCl6, Li3YBr6, Li3ErCl6, Li3InCl6, Li3InBr6.

[0145] Optionally, the oxide solid-state electrolyte material can include one or more of a perovskite-structured oxide solid-state electrolyte material, a garnet-structured oxide solid-state electrolyte material, an oxide solid-state electrolyte material having a NASICON structure, an oxide solid-state electrolyte material having a LISICON structure.

[0146] In some embodiments, the negative current collector can be a metal foil, a three-dimensional porous current collector, or a composite current collector. As a metal foil, pure metals, alloys, surface-treated metals can be used, for example, which can include but are not limited to stainless steel foils, copper foils, copper alloy foils, nickel foils, nickel alloy foils, aluminum foils, aluminum alloy foils. As an example of a three-dimensional porous current collector, copper mesh, nickel mesh, aluminum mesh, foamed copper, foamed nickel, foamed aluminum can be used. The composite current collector can include a polymer material base layer and a metal material layer formed on at least one surface of the polymer material base layer. As an example, the metal material can include but is not limited to one or more of copper, copper alloy, aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver, and silver alloy. As an example, the polymer material base layer can include but is not limited to one or more of polypropylene, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene, and polyethylene.

[0147] [Electrolyte sheet]

[0148] The electrolyte sheet can be prepared by a dry process or by a wet process.

[0149] In some embodiments, the electrolyte sheet can include a solid-state electrolyte material. Optionally, the solid-state electrolyte material can include but is not limited to one or more of a sulfide solid-state electrolyte material, a halide solid-state electrolyte material, an oxide solid-state electrolyte material.

[0150] The types of sulfide solid-state electrolyte materials can refer to the sulfide solid-state electrolyte materials in the positive electrode sheet described above, which will not be repeated here.

[0151] Optionally, the halide solid-state electrolyte material can include one or more of Li3YCl6, Li3YBr6, Li3ErCl6, Li3InCl6, Li3InBr6.

[0152] Optionally, the oxide solid-state electrolyte material can include one or more of a perovskite-structured oxide solid-state electrolyte material, a garnet-structured oxide solid-state electrolyte material, an oxide solid-state electrolyte material having a NASICON structure, an oxide solid-state electrolyte material having a LISICON structure.

[0153] In some embodiments, the electrolyte sheet can also include a binder, or can not include a binder, which can be adjusted according to the preparation process of the solid-state battery cell. Optionally, the binder can include, but is not limited to, one or more of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, fluorine-containing acrylate resin, water-soluble unsaturated resin SR-1B, methyl vinyl silicone rubber, nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), styrene butadiene rubber (SBR), thermoplastic styrene butadiene rubber (SBS), isoprene rubber, butadiene rubber (BR), ethyl cellulose, polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA), carboxymethyl chitosan (CMCS), fluororubber, and acrylate rubber.

[0154] In some embodiments, the solid-state battery cell can also include an outer package for containing the negative electrode sheet, the electrolyte sheet, and the positive electrode sheet. The outer package can be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, and the like. The outer package can also be a soft package, such as a pouch-type soft package. The material of the soft package can be plastic, such as one or more of aluminum-plastic film, polypropylene, polybutylene terephthalate (PBT), and polybutylene succinate (PBS).

[0155] Methods for preparing solid-state battery cells are known, such as, for example, the assembly methods for solid-state battery cells including, but not limited to, button cells, mold cells, hard-shell cells, soft-pack cells, and the like.

[0156] Embodiments

[0157] The following examples describe the present disclosure in more detail, which are merely illustrative and not intended to limit the scope of the present disclosure, as various modifications and variations are obvious to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are based on mass, and all reagents used in the examples are commercially available or synthesized according to conventional methods and used directly without further purification, and the instruments used in the examples are commercially available.

[0158] Example 1

[0159] Preparation of the positive electrode active material

[0160] Li 1.2 Ni 0.13 Co 0.13 Mn 0.54O2 powder and InCl3 powder were added into a mechanical mixing machine, and run at a speed of 3000 rpm for 1 h to coat InCl3 on the surface of Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O2 to obtain a positive electrode active material.

[0161] Preparation of a positive electrode sheet

[0162] The positive electrode active material prepared above, the sulfide solid electrolyte material Li6PS5Cl, the positive electrode conductive agent vapor grown carbon fiber (VGCF), and the positive electrode binder polytetrafluoroethylene (PTFE) were mixed in a double planetary mixer at a solid content mass ratio of 70:26:3:1, and then the mixed material was kneaded into a lump in an internal mixer, and then hot-rolled into a self-supporting electrode sheet at 80°C. Finally, the electrode sheet was hot-rolled with an aluminum foil as the positive electrode current collector to obtain a positive electrode sheet. The average particle size of the sulfide solid electrolyte material Li6PS5Cl was 700 nm.

[0163] Preparation of a solid-state battery cell

[0164] 100 mg of the sulfide solid electrolyte material Li6PS5Cl was weighed and added into a battery mold, and an electrolyte sheet was obtained by pressing. Then, the positive electrode sheet was placed on one side of the electrolyte sheet, and an InLi alloy was added on the other side as the negative electrode. The assembly was pressed at 500 MPa for 5 min to obtain a solid-state battery cell.

[0165] Example 2

[0166] The preparation method of the solid-state battery cell was the same as that of Example 1, except for the following differences.

[0167] Preparation of a positive electrode active material

[0168] Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O2 powder and InCl3 powder were added into a mechanical mixing machine, and run at a speed of 3000 rpm for 1 h to coat InCl3 on the surface of Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O2 to obtain a positive electrode active material.

[0169] Example 3

[0170] The preparation method of the solid-state battery cell was the same as that of Example 1, except for the following differences.

[0171] Preparation of a positive electrode active material

[0172] Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O2powder and InCl3powder were added into a mechanical fusion machine, and run at a speed of 3000 rpm for 1 h to coat InCl3on the surface of Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O2, to obtain a positive electrode active material.

[0173] Example 4

[0174] The preparation method of the solid-state battery monomer was the same as that of Example 1, except for the following differences.

[0175] Preparation of a positive electrode active material

[0176] Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O2powder and In2S3powder were added into a mechanical fusion machine, and run at a speed of 3000 rpm for 1 h to coat In2S3on the surface of Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O2, to obtain a positive electrode active material.

[0177] Example 5

[0178] The preparation method of the solid-state battery monomer was the same as that of Example 1, except for the following differences.

[0179] Preparation of a positive electrode active material

[0180] Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O2powder and In2Se3powder were added into a mechanical fusion machine, and run at a speed of 3000 rpm for 1 h to coat In2Se3on the surface of Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O2, to obtain a positive electrode active material.

[0181] Example 6

[0182] The preparation method of the solid-state battery monomer was the same as that of Example 1, except for the following differences.

[0183] Preparation of a positive electrode active material

[0184] Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O2powder and In2Te3powder were added into a mechanical alloying machine, and run at a speed of 3000 rpm for 1 h to coat In2Te3on the surface of Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O2, and Li3InCl6was added into the mechanical alloying machine and run at a speed of 3000 rpm for 1 h to obtain the positive electrode active material. The positive electrode active material comprises the matrix material Li

[0185] Example 7

[0186] The method for preparing the solid-state battery monomer was the same as that in Example 1, except for the following differences.

[0187] Preparation of the positive electrode active material

[0188] Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O2powder and InCl3powder were added into a mechanical alloying machine, and run at a speed of 3000 rpm for 1 h to coat InCl3on the surface of Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O2, and Li3InCl6was added into the mechanical alloying machine and run at a speed of 3000 rpm for 1 h to obtain the positive electrode active material. The positive electrode active material comprises the matrix material Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O2, InCl3on the surface of the matrix material, and Li3InCl6on the surface of InCl3, wherein the mass fraction of InCl3is 1.5% and the mass fraction of Li3InCl6is 1.5% based on the total mass of the positive electrode active material.

[0189] Example 8

[0190] The method for preparing the solid-state battery monomer was the same as that in Example 1, except for the following differences.

[0191] Preparation of the positive electrode active material

[0192] Li 1.2 Ni 0.13 Co 0.13 Mn 0.54O2 and InCl3 powder were added into a mechanical fusion machine, and run at a speed of 3000 rpm for 1 h to coat InCl3 on the surface of Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O2; Li3InCl6 was further added into the mechanical fusion machine and run at a speed of 3000 rpm for 1 h to obtain the positive electrode active material. The positive electrode active material comprises the base material Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O2, InCl3 on the surface of the base material, and Li3InCl6 on the surface of InCl3. The mass fraction of InCl3 is 0.5%, and the mass fraction of Li3InCl6 is 2.5%, based on the total mass of the positive electrode active material being 100%.

[0193] Example 9

[0194] The preparation method of the solid-state battery monomer was the same as that in Example 1, except for the following differences.

[0195] Preparation of the positive electrode active material

[0196] Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O2 and InCl3 powder were added into a mechanical fusion machine, and run at a speed of 3000 rpm for 1 h to coat InCl3 on the surface of Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O2; Li3InCl6 was further added into the mechanical fusion machine and run at a speed of 3000 rpm for 1 h to obtain the positive electrode active material. The positive electrode active material comprises the base material Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O2, InCl3 on the surface of the base material, and Li3InCl6 on the surface of InCl3. The mass fraction of InCl3 is 0.5%, and the mass fraction of Li3InCl6 is 2.5%, based on the total mass of the positive electrode active material being 100%.

[0197] Comparative Example 1

[0198] Preparation of the positive electrode sheet

[0199] The positive electrode active material Li 1.2 Ni 0.13 Co 0.13 Mn0.54 O2, sulfide solid electrolyte material Li6PS5Cl, positive electrode conductive agent vapor grown carbon fiber (VGCF), positive electrode binder polytetrafluoroethylene (PTFE) were mixed in a double planetary mixer according to a solid content mass ratio of 70:26:3:1, then the uniformly mixed material was kneaded into a lump material in an internal mixer under heating and pressure, and then hot-rolled into a self-supporting electrode sheet at 80°C, and finally the electrode sheet was hot-rolled with a positive electrode current collector aluminum foil to obtain a positive electrode sheet. The average particle size of the sulfide solid electrolyte material Li6PS5Cl was 700 nm.

[0200] Preparation of a solid-state battery monomer

[0201] 100 mg of sulfide solid electrolyte material Li6PS5Cl was weighed into a battery mold, and an electrolyte sheet was obtained by pressing. Then, a positive electrode sheet was placed on one side of the electrolyte sheet, and an InLi alloy was added on the other side as a negative electrode. The solid-state battery monomer was assembled by pressing at 500 MPa for 5 min.

[0202] Comparative Example 2

[0203] The preparation method of the solid-state battery monomer was the same as that of Example 1, except for the following differences.

[0204] Preparation of a positive electrode active material

[0205] Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O2 powder and Li2ZrO3 powder were weighed according to a mass ratio of 97:3, and were mixed uniformly using a dry coating device; the uniformly mixed material was heat-treated at 400°C for 1 h in an oxygen atmosphere to obtain a positive electrode active material.

[0206] Performance test

[0207] (1) First cycle coulombic efficiency test

[0208] At 25°C, the solid-state battery monomer was charged to 4.8 V (vs. Li + / Li) at a current density of 0.1C, and then rested for 10 min. Then, the solid-state battery monomer was discharged to 2.0 V (vs. Li + / Li) at a current density of 0.1C, to obtain the 0.1C first cycle charge specific capacity and the 0.1C first cycle discharge specific capacity.

[0209] First cycle coulombic efficiency (%) = first cycle discharge specific capacity / first cycle charge specific capacity x 100%.

[0210] (2) Cycle performance test

[0211] The solid-state battery monomer was charged to 4.8 V (vs. Li + / Li) at a current density of 0.1 C at 25°C, rested for 10 min, and then discharged to 2.0 V (vs. Li + / Li) at a current density of 0.1 C, and cycled for 3 times; the solid-state battery monomer was then charged to 4.8 V (vs. Li + / Li) at a current density of 0.33 C, rested for 10 min, and then discharged to 2.0 V (vs. Li + / Li) at a current density of 0.33 C, and cycled for 200 times at a current density of 0.33 C, and the discharge specific capacity at this time was recorded as C2.

[0212] The capacity retention rate of the solid-state battery monomer after 200 cycles = C2 / C1 x 100%.

[0213] Table 1

[0214] From the above test results, it can be seen that the positive electrode active material of the present disclosure has a high discharge capacity, and the solid-state battery monomer using the same has a high first-cycle coulombic efficiency and good cycle performance.

[0215] The lithium-rich manganese-based material of Comparative Example 1 was not surface-coated, and its actual discharge capacity was very low, and the cycle performance of the solid-state battery monomer using the same was also poor.

[0216] Comparative Example 2 coated the lithium-rich manganese-based material with an oxide Li2ZrO3, and compared with Comparative Example 1, the actual discharge capacity of the lithium-rich manganese-based material was improved to a certain extent, but the cycle performance of the solid-state battery monomer was still not ideal.

[0217] It should be noted that the present disclosure is not limited to the above embodiments. The above embodiments are only examples, and embodiments having substantially the same configuration and playing the same role and effect as the technical idea within the scope of the technical solutions of the present disclosure are all included in the technical scope of the present disclosure. In addition, within the scope of the main idea of the present disclosure, various modifications that can be thought of by those skilled in the art are applied to the embodiments, and other modes constructed by combining part of the constituent elements in the embodiments are also included in the scope of the present disclosure.

Claims

1. A positive electrode sheet, wherein, The positive electrode sheet comprises a positive electrode active material and a sulfide solid electrolyte material, the positive electrode active material comprises a base material and a coating material on at least part of the surface of the base material, the base material comprises a lithium-rich manganese-based material, and the coating material comprises one or more of indium halide, indium sulfide In2S3, indium selenide In2Se3, and indium telluride In2Te3.

2. The positive electrode sheet according to claim 1, wherein, the mass fraction of the coating material is 0.1%-5% based on the total mass of the positive electrode active material; and / or, the thickness of the coating material is 0.5 nm-50 nm.

3. The positive electrode sheet according to claim 1, wherein The coating material comprises a first coating material and a second coating material, the first coating material is on at least part of the surface of the base material, and the second coating material is on at least part of the surface of the first coating material, the first coating material comprises one or more of indium halide, indium sulfide In2S3, indium selenide In2Se3, and indium telluride In2Te3, and the second coating material comprises an indium-containing halide solid electrolyte material.

4. The positive electrode sheet according to claim 3, wherein Li3InCl6, Li2In a Sc (2- a) / 3 Cl4, Li3Y 1-b In b Cl6, Li 3-c In 1-c Zr c Cl6, one or more of Li3InCl6, Li2In 5. The positive electrode sheet according to any one of claims 3-4, wherein, the mass fraction of the coating material is 0.1%-5% based on the total mass of the positive electrode active material; and / or, the thickness of the coating material is 0.5 nm-50 nm.

6. The positive electrode sheet according to any one of claims 3 to 5, wherein The mass ratio of the first coating material to the second coating material is 0.02:1 to 50:

1.

7. The positive electrode sheet according to any one of claims 3 to 6, wherein The ratio of the thickness of the coating layer formed by the first coating material to the thickness of the coating layer formed by the second coating material is 0.01:1 to 100:

1.

8. The positive electrode sheet according to any one of claims 1 to 7, wherein The coating material is on 90%-100% of the surface of the base material.

9. The positive electrode sheet according to any one of claims 1-8, wherein, the mass ratio of the positive electrode active material to the sulfide solid electrolyte material is 99:1 to 50:50; and / or, the average particle size of the positive electrode active material is 0.5 μm-10 μm; and / or, the average particle size of the sulfide solid electrolyte material is 50 nm-1000 nm.

10. The positive electrode sheet according to any one of claims 1 to 9, wherein The positive electrode sheet further comprises a positive electrode conductive agent and / or a positive electrode binder.

11. The positive electrode sheet according to any one of claims 1 to 10, wherein The positive electrode sheet further comprises a positive electrode current collector, and the positive electrode active material and the sulfide solid electrolyte material are on at least one surface of the positive electrode current collector.

12. A solid-state battery monomer comprising a negative electrode sheet, an electrolyte sheet, and the positive electrode sheet according to any one of claims 1-11, wherein the electrolyte sheet is between the negative electrode sheet and the positive electrode sheet.

13. The solid-state battery monomer according to claim 12, wherein, the negative electrode sheet comprises one or more of lithium, lithium alloy, natural graphite, artificial graphite, mesophase carbon microbeads, soft carbon, hard carbon, silicon-based material, tin-based material, lithium titanate, and metal oxide; and / or, the electrolyte sheet comprises a solid electrolyte material.

14. A battery device comprising a plurality of solid-state battery monomers according to any one of claims 12-13.

15. An electric device comprising the solid-state battery cell of any one of claims 12-13 or the battery device of claim 14.

16. A positive electrode active material, wherein, The positive active material comprises a base material and a coating material on at least part of the surface of the base material, the base material comprises a lithium-rich manganese-based material, and the coating material comprises one or more of indium halide, indium sulfide In2S3, indium selenide In2Se3, and indium telluride In2Te3.

17. The positive electrode active material according to claim 16, wherein The coating material comprises a first coating material and a second coating material, the first coating material is on at least part of the surface of the base material, and the second coating material is on at least part of the surface of the first coating material, the first coating material comprises one or more of indium halide, indium sulfide In2S3, indium selenide In2Se3, and indium telluride In2Te3, and the second coating material comprises an indium-containing halide solid-state electrolyte material.

18. The positive electrode active material according to claim 17, wherein Li3InCl6, Li2In a Sc (2-a) / 3 Cl4, Li3Y 1-b In b Cl6, Li 3-c In 1-c Zr c Cl6, 0 < a < 1, 0 < b < 1, 0 < c < 1.

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