Solid-state battery material, positive electrode active material layer, positive electrode film, solid-state electrolyte membrane, solid-state battery, electric device, and application

Abstract

The present application relates to a solid-state battery material, a positive electrode active material layer, a positive electrode film, a solid-state electrolyte membrane, a solid-state battery, an electric device, and an application. The solid-state battery material comprises coated particles. Each coated particle comprises a particle body and an oxygen storage layer located on at least a portion of the surface of the particle body, and the oxygen storage layer comprises an oxygen storage material. The coated particles are at least one of coated positive electrode active particles and coated electrolyte particles.

Description

Solid-state battery materials, positive electrode active material layers, positive electrode films, solid electrolyte membranes, solid-state batteries, electrical devices, and applications

[0001] Related applications

[0002] This application claims priority to Chinese patent application number CN2024102711459, filed on March 8, 2024, entitled “Solid-state battery materials, positive electrode active material layer, positive electrode film, solid electrolyte membrane, solid-state battery, electrical device and application,” the entire text of which is hereby incorporated by reference. Technical Field

[0003] The present application relates to the field of solid-state battery technology, and further to solid-state battery materials, positive electrode active material layers, positive electrode membranes, solid electrolyte membranes, solid-state batteries, electrical devices, and applications. Background Art

[0004] The statements herein merely provide background information related to the present application and do not necessarily constitute prior art.

[0005] Solid-state batteries use non-flammable solid electrolytes instead of the organic electrolytes found in traditional liquid secondary batteries, significantly improving battery safety. They are considered the next generation of batteries closest to industrialization. Comprehensively improving the discharge capacity and cycle performance of solid-state batteries is crucial for their industrialization.

[0006] Summary of the Invention

[0007] According to various embodiments and examples of the present application, the present application provides a solid-state battery material, a positive electrode active material layer, a positive electrode film, a solid electrolyte membrane, a solid-state battery, an electrical device, and applications. The solid-state battery material is provided with an oxygen storage layer, and using the solid-state battery material as a raw material can improve the discharge capacity and cycle performance of sulfide solid-state batteries.

[0008] In a first aspect of the present application, a solid-state battery material is provided, comprising a coated particle, wherein the coated particle comprises a particle body and an oxygen storage layer located at at least a portion of a surface of the particle body, wherein the oxygen storage layer comprises an oxygen storage material;

[0009] Wherein, the coated particles are at least one of coated positive electrode active particles and coated electrolyte particles;

[0010] When the coated particles are the coated positive electrode active particles, the particle body is a positive electrode active body, and the positive electrode active body contains a positive electrode active material;

[0011] When the coated particles are the coated electrolyte particles, the particle body is a solid electrolyte body, and the solid electrolyte body contains a sulfide electrolyte.

[0012] This solid-state battery material can be used as a sulfide solid-state battery material, and the solid-state battery material includes coated particles provided with a surface oxygen storage layer, so that the oxygen storage layer is located on at least a portion of the surface of the coated particles; the coated particles can be positive electrode active particles coated with a surface oxygen storage layer, or can be sulfide-based electrolyte particles coated with a surface oxygen storage layer, or can be a combination of the two coated particles coated with a surface oxygen storage layer. When using this solid-state battery material to prepare a sulfide solid-state battery, the oxygen storage material in the oxygen storage layer absorbs oxygen, which can reduce the contact probability between the sulfide electrolyte and oxygen, thereby improving the chemical stability of the sulfide electrolyte during the battery preparation process, and is conducive to giving full play to the rapid ion conduction function of the sulfide electrolyte, thereby promoting the stable operation of the solid-state battery and improving the discharge capacity and cycle performance of the sulfide solid-state battery.

[0013] For the coated electrolyte particles, they include a solid electrolyte body and an oxygen storage layer located at least in part of the surface of the solid electrolyte body, the solid electrolyte body includes a sulfide electrolyte, and the oxygen storage layer includes an oxygen storage material. It can be seen that the coated electrolyte particles are sulfide-based electrolyte particles with an oxygen storage layer provided on their surface. The coated electrolyte particles can be used as a solid electrolyte in the solid electrolyte layer of a solid-state battery, or as a solid electrolyte in an electrode active material layer, for example, as a solid electrolyte in a positive electrode active material layer. When the coated electrolyte particles are used to prepare a separate solid electrolyte membrane or positive electrode membrane, or when a positive electrode layer is formed on a base membrane (such as a solid electrolyte membrane), and in the process of preparing a solid-state battery using a membrane containing the coated electrolyte particles, the oxygen storage layer provided on the surface of the coated electrolyte particles can play a role in protecting the sulfide electrolyte, which can reduce or isolate the decomposition effect of oxygen in the air on the sulfide electrolyte, thereby improving the chemical stability of the sulfide electrolyte in the battery preparation process, which is beneficial for the sulfide electrolyte to fully exert its fast ion conduction function, promote the stable operation of the solid-state battery, and improve the discharge capacity and cycle performance of the sulfide solid-state battery. Furthermore, the oxygen storage layer provided on the surface of the coated electrolyte particles can also reduce or isolate direct contact between the sulfide electrolyte and moisture in the air, inhibiting the decomposition of the sulfide electrolyte and the generation of hydrogen sulfide gas, thereby improving the chemical stability of the sulfide electrolyte. Thus, by providing an oxygen storage layer on the surface of the sulfide electrolyte, the oxygen storage material in the oxygen storage layer can absorb and store oxygen, and furthermore, it can block direct contact between the sulfide electrolyte and moisture, thereby giving the coated electrolyte particles better air stability.

[0014] The coated positive electrode active particles include a positive electrode active body and an oxygen storage layer located on at least a portion of the surface of the positive electrode active body. The positive electrode active body includes a positive electrode active material, and the oxygen storage layer includes an oxygen storage material. Therefore, the coated positive electrode active particles are positive electrode active particles with an oxygen storage layer disposed on their surface. The coated positive electrode active particles can provide the positive electrode active material in the positive electrode layer of the solid-state battery. For solid-state batteries, generally, positive electrode electrolyte particles are provided on the positive electrode active material layer of the positive electrode layer to play the role of accelerating ion conduction, reducing interface impedance, and giving full play to the capacity of the positive electrode active particles. When the positive electrode electrolyte particles are sulfide-based electrolytes, that is, containing sulfide electrolytes, in the process of preparing the positive electrode film, the positive electrode layer of the solid-state battery, and preparing the solid-state battery, the oxygen storage layer provided on the surface of the positive electrode active particles can absorb and store oxygen, which can reduce or isolate the attack and decomposition of oxygen in the air on the sulfide electrolyte, thereby promoting the stable operation of the solid-state battery, and is conducive to the sulfide electrolyte to give full play to its role of rapid ion conduction, reduce interface resistance, promote the stable operation of the solid-state battery, and improve the discharge capacity and cycle performance of the sulfide solid-state battery. In addition, it can also improve the rate performance of the solid-state battery. It can be seen that by providing an oxygen storage layer on the surface of the positive electrode active material, it can also play a role in protecting the sulfide-based electrolyte used in combination with it, thereby improving the air stability of the positive electrode electrolyte particles and the positive electrode layer, thereby improving the aforementioned electrochemical properties of the solid-state battery.

[0015] In some embodiments, the oxygen storage material includes one or more of a lanthanide metal oxysulfate-type oxygen storage material, a yttrium barium cobalt oxide-type oxygen storage material, and a perovskite-type oxygen storage material.

[0016] In some embodiments, the oxygen storage material satisfies one or more of the following characteristics:

[0017] The lanthanide metal oxysulfate type oxygen storage material includes a chemical formula of Ln2O2SO 4-δ1 Oxygen storage material, wherein Ln is a lanthanide metal element, the lanthanide metal element includes one or more elements of La, Ce, Pr, Nd, Sm, Eu, Gd and Tb, 0≤δ1≤4;

[0018] The yttrium barium cobalt oxide type oxygen storage material includes a chemical formula of (Y x M1 (1-x) )(Ba y M2 (1-y) )(Co z M3 (1-z) )4O 7+δ2Oxygen storage material, wherein M1 is selected from one or more elements of Ca, In, Dy, Ho, Er, Tm, Yb and Lu, M2 is Sr, M3 is selected from one or more elements of Mn, Fe, Ni, Cu, Zn, Al, Ga and Zr, 0≤x≤1, 0≤y≤1, 0≤z≤1, 0≤δ2≤1.5;

[0019] The perovskite oxygen storage material includes a chemical formula of La 1-a A a Mn 1-b B b O 3-δ3 Oxygen storage material, wherein A is selected from one or more elements of Sr, Y, Ce, Pr and Nd, B is selected from one or more elements of Ni, Fe, Cu and Co, 0≤a≤1, 0≤b≤1, 0≤δ3≤1.

[0020] The aforementioned types of oxygen storage materials can be selected to form an oxygen storage layer on the surface of the positive electrode active body or the solid electrolyte body, both of which can improve the chemical stability of the sulfide electrolyte during battery preparation, and are beneficial to improving the discharge capacity and cycle performance of the sulfide solid-state battery.

[0021] In some embodiments, the weight percentage of the oxygen storage material in the coated particles is 0.1 wt% to 10 wt%, and can be optionally 0.5 wt% to 5 wt%.

[0022] In some embodiments, the thickness of the oxygen storage layer is 0.1 nm to 50 nm, and can be optionally 0.5 nm to 10 nm.

[0023] By controlling either the weight percentage of the oxygen storage material in the coated particles or the thickness of the oxygen storage layer, the amount of oxygen storage material coated can be adjusted. It is understood that adjusting both parameters simultaneously can also adjust the amount of oxygen storage material coated. By controlling at least one of the weight percentage of the oxygen storage material in the coated particles and the thickness of the oxygen storage layer within the aforementioned range, not only is it beneficial to improve the stability of the sulfide electrolyte components involved in the solid-state battery preparation process, but it also helps the sulfide electrolyte fully utilize its rapid ion conductivity.

[0024] In some embodiments, the oxygen storage material includes oxygen storage particles; the particle size of the oxygen storage particles is 1 nm to 100 nm, and can be optionally 1 nm to 50 nm.

[0025] The oxygen storage material in the oxygen storage layer can be granular oxygen storage particles. In this case, the specific surface area of ​​the oxygen storage particles can be adjusted by controlling the particle size of the oxygen storage particles. Controlling the particle size within the aforementioned range helps the particles have a larger oxygen-absorbing surface area, allowing the oxygen storage material to better perform its aforementioned function of absorbing and storing oxygen, while also further facilitating its ability to isolate moisture from the air.

[0026] In some embodiments, the particle size of the positive electrode active body is 0.1 μm to 20 μm, and can be optionally 1 μm to 10 μm.

[0027] In some embodiments, the D coating the positive electrode active particles v 50 is 0.1μm~20μm, and can be selected as 1μm~10μm; among them, D v 50 represents the particle size corresponding to when the cumulative volume distribution percentage of the multi-particle mixture reaches 50%.

[0028] By adjusting the D v 50 and at least one of the particle size of the positive electrode active body can adjust the size of the coated positive electrode active particles. v Controlling at least one of the parameters of the particle size of the active cathode particles (50 and the particle size of the active cathode particles) within the aforementioned ranges is beneficial for improving the discharge capacity of the coated active cathode particles and maintaining good contact between the coated active cathode particles and the sulfide-based electrolyte within the composite positive electrode. Smaller coated active cathode particles have shorter active ion transport channels within them, which is beneficial for improving the discharge capacity of the coated active cathode particles themselves. Larger coated active cathode particles are better encapsulated by the sulfide-based electrolyte, providing better interfacial contact with the sulfide-based electrolyte and improving battery cycling performance. Coated active cathode particles of relatively moderate size can enable batteries to achieve both high discharge capacity and excellent cycling performance.

[0029] In some embodiments, the positive electrode active material includes an oxide positive electrode active material;

[0030] Optionally, the oxide positive electrode active material includes lithium transition metal oxide.

[0031] In some embodiments, the lithium transition metal oxide includes one or more of a lithium cobalt oxide-type positive electrode active material, a high nickel positive electrode active material, a lithium-rich manganese-based positive electrode active material, and a modified form of any of the foregoing positive electrode active materials; the modified form includes one or more of a doping modification and a coating modification;

[0032] Optionally,

[0033] The lithium cobalt oxide type positive electrode active material comprises Li, Co and O, wherein the atomic molar ratio of Co to O is x2:2, and satisfies 0.9≤x2≤1; alternatively, the lithium cobalt oxide type positive electrode active material comprises Li, Co and O in an atomic molar ratio of 1:x2:2, and satisfies 0.9≤x2≤1;

[0034] The high-nickel positive electrode active material comprises Li, Ni and O, wherein the atomic molar ratio of Ni to O is y2:2, and satisfies 0.6≤y2≤1; alternatively, the high-nickel positive electrode active material comprises Li, Ni and O in an atomic molar ratio of 1:y2:2, and satisfies 0.6≤y2≤1;

[0035] The lithium-rich manganese-based positive electrode active material comprises Li, Mn and O elements in an atomic molar ratio of (1+p): (p+r(1-p)): (2+p), and satisfies 0 <p≤1,0≤r≤1。

[0036] In some embodiments, the lithium transition metal oxide satisfies one or more of the following characteristics:

[0037] 0.8≤y2≤1;

[0038] 0.2≤p≤1.

[0039] In some embodiments, the lithium transition metal oxide satisfies one or more of the following characteristics:

[0040] The lithium cobalt oxide positive electrode active material includes a chemical formula of LiCo x2 R 1-x2 O2 lithium transition metal oxide, R is selected from one or more elements of Ni, Mg, Ti, Al, Cr, Fe, Nb and Ta;

[0041] The high nickel positive electrode active material includes a chemical formula of LiNi y2 Co z2 D 1-y2-z2 A lithium transition metal oxide of O2, 0≤z2≤0.4, 0.6≤(y2+z2)≤1, D is selected from one or more elements of Mn, Al, Zr, La, Ce, Ti, Mg, Nb, Ta, Mo and W; optionally, D includes Mn;

[0042] The lithium-rich manganese-based positive electrode active material includes a lithium transition metal oxide with a chemical formula of pLi2MnO3·(1-p)LiZO2, where Z is selected from one or more elements of Ni, Co, Mn, Cr, Fe, Al, Nb, Mo and Ru.

[0043] When the positive electrode active material in the positive electrode active particles includes an oxide positive electrode active material (such as a lithium transition metal oxide), the oxide positive electrode active material may release oxygen at high operating voltages. By providing the aforementioned solid-state battery material in the positive electrode active material layer containing the oxide positive electrode active material (such as a lithium transition metal oxide), direct contact between the oxide positive electrode active material and the sulfide electrolyte can be hindered. The oxygen storage material absorbs the oxygen that may be released by the positive electrode, thereby inhibiting the attack of the released oxygen on the sulfide electrolyte, thereby reducing the oxidative decomposition of the sulfide electrolyte by oxygen. This can inhibit the interfacial side reactions between the oxide positive electrode active material (such as a lithium transition metal oxide) and the sulfide electrolyte, inhibiting the increase in interfacial impedance, and facilitating the improvement of the stability of the sulfide electrolyte in the positive electrode layer during the cycling of the sulfide solid-state battery, thereby maintaining its excellent electrical conductivity, facilitating the long-term ionic conduction of the sulfide electrolyte and fully utilizing the capacity of the positive electrode active particles, and endowing the sulfide solid-state battery with excellent high-voltage stability. Furthermore, the sulfide solid-state battery can have a higher first coulombic efficiency, a higher discharge capacity, a higher rate capability, and better cycling performance. In addition, when a certain concentration of oxygen is stored in the oxygen storage material, the oxygen partial pressure on the surface of the positive electrode material increases, thereby further hindering the release of oxygen from the positive electrode material, thereby enhancing the structural stability of the positive electrode material.

[0044] When the positive electrode active material in the positive electrode active particles includes an oxide positive electrode active material (such as a lithium transition metal oxide), by adjusting at least one parameter of the weight ratio of the oxygen storage material in the coated particles and the thickness of the oxygen storage layer, it is possible to achieve both the suppression of oxygen release and good interfacial ion transport. This can not only suppress oxygen release, improve the stability of the sulfide electrolyte, and achieve good discharge capacity and cycle performance, but also achieve good interfacial ion transport and fully utilize the discharge capacity of the positive electrode layer.

[0045] When the positive electrode active material in the positive electrode active particles includes an oxide positive electrode active material (such as a lithium transition metal oxide), by adjusting the D v 50 and at least one of the particle size of the positive electrode active body, the amount of the oxygen storage material in the oxygen storage layer relative to the positive electrode active material contained in the positive electrode active body can also be indirectly adjusted. v At least one parameter of the particle size of the positive electrode active body is controlled within the above range, which is beneficial for the oxygen storage material to provide sufficient oxygen absorption capacity, and is also beneficial for improving the discharge capacity of the coated positive electrode active particles and maintaining good contact between the coated positive electrode active particles and the sulfide-based electrolyte in the composite positive electrode.

[0046] Lithium transition metal oxides such as lithium cobalt oxide-type positive electrode active materials, high nickel positive electrode active materials, and lithium-rich manganese-based positive electrode active materials easily release oxygen at high operating voltages. When these lithium transition metal oxides are used as positive electrode active materials in positive electrode active particles, by arranging the aforementioned solid-state battery materials in the positive electrode active material layer, it is beneficial to achieve both high energy density and long cycle performance of sulfide solid-state batteries while allowing for the possibility of positive electrode oxygen release.

[0047] When the solid-state battery material provided in the positive electrode active material layer includes the aforementioned coated positive electrode active particles, it is further beneficial to inhibit the release of oxygen from the positive electrode material, improve the crystal structure stability of the positive electrode active particles during battery cycling, inhibit the formation of surface rock salt phase, and is beneficial to fully utilize the positive electrode capacity and improve the long-cycle performance of the battery.

[0048] In some embodiments, the particle size of the solid electrolyte body is 1 nm to 20 μm, and can be optionally 50 nm to 5 μm.

[0049] In some embodiments, the D of the coated electrolyte particles v 50 is 1nm~20μm, and can be selected as 50nm~5μm; among them, D v 50 represents the particle size corresponding to when the cumulative volume distribution percentage of the multi-particle mixture reaches 50%.

[0050] By adjusting the D v 50 and the particle size of the solid electrolyte body can adjust the size of the coated electrolyte particles. v Regulating at least one of the particle size of the solid electrolyte particles (50) and the particle size of the solid electrolyte body within the aforementioned range is beneficial for improving the overall ion conductivity of the film layer in which the coated electrolyte particles are located, providing a better electrical contact network, and taking into account manufacturing costs. This can adjust the manufacturing cost of the solid electrolyte body and the amount of oxygen storage material required to prepare the coated electrolyte particles. A relatively small particle size of the coated electrolyte particles is beneficial for improving the electrical contact between the positive electrode active particles within the positive electrode film or positive electrode layer, thereby promoting the full capacity of the solid-state battery. A relatively moderate particle size of the coated electrolyte particles is easier to manufacture.

[0051] In some embodiments, the sulfide electrolyte includes one or more of an argyrodite-type sulfide electrolyte, an LGPS-type sulfide electrolyte, and a lithium sulfide pentasulfide diphosphorus complex-type sulfide electrolyte.

[0052] In some embodiments, the sulfide electrolyte satisfies one or more of the following characteristics:

[0053] The argyrodite-type electrolyte includes a chemical formula of Li 6±s P1-j A j S 5±s-t B t X 1±s sulfide electrolyte of, where 0 ≤ j < 1, 0 ≤ t < 1, 0 ≤ s < 1, A is selected from one or more elements of Ge, Si, Sn, and Sb, B is one or more elements of O, Se, and Te, and X is selected from one or more elements of Cl, Br, I, and F;

[0054] The LGPS-based sulfide electrolyte includes a chemical formula of Li 10±δ5 Ge 1-g G g P 2-q Q q S 12-w W w sulfide electrolyte of, where 0 ≤ δ5 < 1, 0 ≤ g ≤ 1, 0 ≤ q ≤ 2, 0 ≤ w < 1, G is selected from one or two elements of Si and Sn, Q is Sb, and W is selected from one or more elements of O, Se, Te, Cl, Br, I, and F;

[0055] The lithium sulfide phosphorus pentasulfide complex-based sulfide electrolyte includes a chemical formula of (100 - u - v)Li2S·uP2S5·vM m N n sulfide electrolyte of, where 0 < u < 100, 0 ≤ v < 100, 0 ≤ u + v < 100, 0 ≤ m < 4, 0 ≤ n < 6, M is selected from one or more elements of Li, B, Ge, Si, Sn, and Sb, and N is selected from one or more elements of S, Se, Te, O, Cl, Br, I, and F.

[0056] By using the foregoing solid-state battery materials, sulfide electrolytes with high ion transport rates can be more flexibly used in sulfide solid-state batteries, greatly reducing the material selection limitations of sulfide electrolytes.

[0057] In some embodiments, the solid-state battery material is a sulfide solid-state battery material.

[0058] In some embodiments, the solid-state battery material is a sulfide all-solid-state battery material.

[0059] In a second aspect of the present application, a positive electrode active material layer is provided, which includes the solid-state battery material described in the first aspect of the present application.

[0060] The positive electrode active material layer provided in the second aspect of the present application includes at least one of coated positive electrode active particles and coated electrolyte particles. When the positive electrode active material layer is applied to a sulfide solid-state battery, the oxygen storage material in the oxygen storage layer absorbs oxygen, which can reduce the contact probability between the sulfide electrolyte and oxygen, thereby improving the chemical stability of the sulfide electrolyte during the battery preparation process, and is conducive to giving full play to the role of the sulfide electrolyte in rapid ion conduction, thereby promoting the stable operation of the solid-state battery and improving the discharge capacity and cycle performance of the sulfide solid-state battery. In addition, the oxygen storage layer provided on the surface of the coated electrolyte particles can also reduce or isolate the direct contact between the sulfide electrolyte and moisture in the air, inhibit the decomposition of the sulfide electrolyte and the generation of hydrogen sulfide gas, and is conducive to improving the chemical stability of the sulfide electrolyte.

[0061] In some embodiments, the positive electrode active material layer includes positive electrode active particles; the positive electrode active particles include the coated positive electrode active particles, and the weight proportion of the coated positive electrode active particles in the positive electrode active material layer is 70wt% to 99wt%, optionally 80wt% to 95wt%.

[0062] In some embodiments, the positive electrode active material layer includes positive electrode electrolyte particles; the positive electrode electrolyte particles include the coated electrolyte particles, and the weight proportion of the coated electrolyte particles in the positive electrode active material layer is 0.1wt% to 30wt%, optionally 5wt% to 20wt%.

[0063] By controlling the weight ratio of the coated positive electrode active particles in the positive electrode active material layer within the above range, it is beneficial to achieve both high energy density and cycle stability.

[0064] When the positive electrode active material layer also includes a sulfide-based electrolyte, by controlling the weight proportion of the coated positive electrode active particles in the positive electrode active material layer within the above range, it is also beneficial to achieve a balance between high energy density and reducing the oxidative decomposition of the sulfide electrolyte contained in the sulfide-based electrolyte.

[0065] The weight percentage of the coated electrolyte particles in the positive electrode active material layer can be controlled within the aforementioned range, which is beneficial for the positive electrode film to provide better overall ion conductivity.

[0066] In the third aspect of the present application, a positive electrode film is provided, which includes a positive electrode active material layer, wherein the positive electrode active material layer includes the solid-state battery material described in the first aspect of the present application, or the positive electrode active material layer is the positive electrode active material layer described in the second aspect of the present application.

[0067] The positive electrode film includes the positive electrode active material layer described in the second aspect of the present application.

[0068] In a fourth aspect of the present application, a solid electrolyte membrane is provided, which includes the solid-state battery material described in the first aspect of the present application, and the coated particles are the coated electrolyte particles.

[0069] This solid electrolyte membrane includes coated electrolyte particles. The oxygen storage layer arranged on the surface of the coated electrolyte particles can reduce or isolate the decomposition effect of oxygen in the air on the sulfide electrolyte, and can also reduce or isolate the direct contact between the sulfide electrolyte and moisture in the air, and can inhibit the decomposition of the sulfide electrolyte and the generation of hydrogen sulfide gas, thereby improving the chemical stability of the sulfide electrolyte in the battery preparation process and the stability of the ion conductivity of the solid electrolyte membrane, promoting the stable operation of the solid-state battery, and being beneficial to improving the discharge capacity and cycle performance of the sulfide solid-state battery.

[0070] In a fifth aspect of the present application, a solid-state battery is provided, which includes the solid-state battery material described in the first aspect of the present application.

[0071] In some embodiments, a solid-state battery is provided, comprising a cathode layer, a solid electrolyte layer, and an anode layer;

[0072] The solid-state battery meets one or more of the following characteristics:

[0073] The positive electrode layer includes the positive electrode active material layer described in the second aspect of the present application;

[0074] The positive electrode layer includes the positive electrode film described in the third aspect of the present application;

[0075] The solid electrolyte layer includes the solid electrolyte membrane described in the fourth aspect of the present application.

[0076] In some embodiments, a solid-state battery is provided, comprising a positive electrode layer, a solid electrolyte layer, and a negative electrode layer;

[0077] The solid-state battery comprises one or more solid-state battery materials described in the first aspect of the present application;

[0078] When the coated particles include the coated positive electrode active particles, the coated positive electrode active particles are located in the positive electrode layer;

[0079] When the coated particles include the coated electrolyte particles, the coated electrolyte particles are located in at least one of the positive electrode layer and the solid electrolyte layer.

[0080] In some embodiments, a solid-state battery is provided, comprising a positive electrode layer, a solid electrolyte layer, and a negative electrode layer; the positive electrode layer comprises a positive electrode active material layer, the positive electrode active material layer comprising positive electrode active particles and positive electrode electrolyte particles;

[0081] At least one of the solid electrolyte layer and the positive electrode electrolyte particles comprises a sulfide electrolyte;

[0082] The solid-state battery comprises one or more solid-state battery materials described in the first aspect of the present application;

[0083] The solid-state battery satisfies at least one of the following characteristics:

[0084] At least a portion of the positive electrode electrolyte particles contain a sulfide electrolyte, and the positive electrode active material layer includes at least one of the coated positive electrode active particles and the coated electrolyte particles;

[0085] The solid electrolyte layer includes the coated electrolyte particles.

[0086] In some embodiments, the solid-state battery satisfies one or more of the following characteristics:

[0087] The solid electrolyte layer and the positive electrode electrolyte particles both contain a sulfide electrolyte, the sulfide electrolyte contained in the positive electrode electrolyte particles is recorded as a first sulfide electrolyte, and the sulfide electrolyte contained in the solid electrolyte layer is recorded as a second sulfide electrolyte, and the first sulfide electrolyte and the second sulfide electrolyte may be the same or different;

[0088] The positive electrode electrolyte particles include a sulfide electrolyte, and at least one of the positive electrode active particles and the positive electrode electrolyte particles includes the coated particles.

[0089] As mentioned above, for a solid-state battery (sulfide solid-state battery) in which the aforementioned solid-state battery material is arranged at at least one of the positive electrode layer and the solid electrolyte layer, when at least one of coated positive electrode active particles and coated electrolyte particles is used in the positive electrode layer, or when coated electrolyte particles are used in the solid electrolyte layer, or when the aforementioned solid-state battery material is used in both the positive electrode layer and the solid electrolyte layer, it is beneficial to improve the discharge capacity and cycle performance of the solid-state battery.

[0090] In some embodiments, the solid-state battery is a sulfide solid-state battery.

[0091] In some embodiments, the solid-state battery is a sulfide all-solid-state battery.

[0092] In the sixth aspect of the present application, an electrical device is provided, which includes the solid-state battery described in the fourth aspect of the present application.

[0093] In the seventh aspect of the present application, there is provided the use of the solid-state battery material described in the first aspect of the present application, or the positive electrode active material layer described in the second aspect of the present application, or the positive electrode film described in the third aspect of the present application, or the solid electrolyte membrane described in the fourth aspect of the present application in the preparation of a solid-state battery; optionally, the solid-state battery is a sulfide solid-state battery; further optionally, the solid-state battery is a sulfide all-solid-state battery.

[0094] The details of one or more embodiments or examples of the present application are set forth in the following drawings and description. Other features, objects, and advantages of the present application will become apparent from the description, drawings, and claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0095] In order to better describe and illustrate the embodiments, examples or examples provided in this application, reference may be made to one or more of the accompanying drawings. The additional details or examples used to describe the accompanying drawings should not be considered as limiting the scope of the disclosed application, the embodiments, examples or examples currently described, and any of the best modes of these applications currently understood. It should also be noted that the accompanying drawings are drawn in a simplified form and are only used to assist in the explanation of this application for convenience and clarity. The various dimensions of each component shown in the accompanying drawings are arbitrarily shown and may be accurate or not drawn to scale. For example, in order to make the illustration clearer, the dimensions of the components are appropriately exaggerated in some places in the accompanying drawings. Unless otherwise specified, the components in the drawings are not drawn to scale. The drawings of this application do not limit every dimension of each component. Moreover, the same figure numbers are used to represent the same components in all the drawings. In the drawings:

[0096] Figure 1 is a schematic structural diagram of coated particles in a solid-state battery material provided in one embodiment of the present application. The coated particles include a particle body and an oxygen storage layer located on the surface of the particle body.

[0097] Figure 2 is a schematic structural diagram of coated particles in a solid-state battery material provided in one embodiment of the present application. The coated particles include a particle body and an oxygen storage layer located on the surface of the particle body, and the oxygen storage layer includes an oxygen storage material.

[0098] Figure 3 is a schematic structural diagram of two types of coated particles involved in some embodiments of the present application, one is a coated positive electrode active particle, and the other is a coated electrolyte particle; the coated positive electrode active particle includes a positive electrode active body and an oxygen storage layer located on the surface of the positive electrode active body, and the oxygen storage layer includes an oxygen storage material; the coated electrolyte particle includes a solid electrolyte body and an oxygen storage layer located on the surface of the solid electrolyte body, and the oxygen storage layer includes an oxygen storage material.

[0099] FIG4 is a schematic structural diagram of a positive electrode active material layer in some embodiments of the present application, wherein the positive electrode active material layer includes coated electrolyte particles.

[0100] FIG5 is a schematic structural diagram of a positive electrode active material layer in some embodiments of the present application, wherein the positive electrode active material layer includes coated positive electrode active particles.

[0101] FIG6 is a schematic structural diagram of a positive electrode active material layer in some embodiments of the present application, wherein the positive electrode active material layer includes coated electrolyte particles and coated positive electrode active particles.

[0102] FIG7 is a schematic structural diagram of a positive electrode active material layer in some embodiments of the present application, wherein the positive electrode active material layer includes coated positive electrode active particles and a sulfide-based electrolyte without an oxygen storage layer.

[0103] FIG8 is a schematic structural diagram of a positive electrode active material layer in some embodiments of the present application, wherein the positive electrode active material layer includes coated electrolyte particles and positive electrode active particles without an oxygen storage layer.

[0104] FIG9 is a schematic structural diagram of a solid electrolyte membrane in some embodiments of the present application, wherein the solid electrolyte membrane is a solid electrolyte membrane including coated electrolyte particles.

[0105] FIG10 is a schematic diagram of the structure of a solid electrolyte membrane used in solid-state batteries provided in some embodiments of the present application. The solid electrolyte membrane is a solid electrolyte membrane including a sulfide-based electrolyte without an oxygen storage layer.

[0106] FIG11 is a schematic structural diagram of a solid electrolyte layer in a solid-state battery provided in some embodiments of the present application, wherein the solid electrolyte layer is a solid electrolyte layer comprising coated electrolyte particles.

[0107] FIG12 is a schematic structural diagram of a solid electrolyte layer in a solid-state battery provided in some embodiments of the present application, wherein the solid electrolyte layer is a solid electrolyte layer comprising a sulfide-based electrolyte without an oxygen storage layer.

[0108] FIG13 is a schematic structural diagram of a positive electrode film according to an embodiment of the present application, wherein the positive electrode film includes a positive electrode current collector and a positive electrode active material layer located on one side of the positive electrode current collector.

[0109] FIG14 is a schematic structural diagram of a positive electrode film according to an embodiment of the present application, wherein the positive electrode film includes a positive electrode current collector and positive electrode active material layers located on both sides of the positive electrode current collector.

[0110] FIG15 is a schematic structural diagram of a solid-state battery cell according to an embodiment of the present application, wherein the solid-state battery cell includes a positive electrode layer, a solid electrolyte layer, and a negative electrode layer stacked in sequence.

[0111] Figure 16 is a structural schematic diagram of an embodiment of the solid-state battery cell shown in Figure 15, which includes a positive electrode layer, a solid electrolyte layer and a negative electrode layer stacked in sequence, wherein the positive electrode layer includes a positive electrode film according to an embodiment of the present application, the positive electrode film includes a positive electrode current collector and a positive electrode active material layer located on both sides of the positive electrode current collector, and a positive electrode active material layer is arranged between the positive electrode current collector and the solid electrolyte layer.

[0112] FIG17 is a schematic diagram of a solid-state battery cell according to an embodiment of the present application.

[0113] FIG18 is an exploded view of the solid-state battery cell according to one embodiment of the present application shown in FIG17 .

[0114] FIG19 is a schematic diagram of a battery module according to an embodiment of the present application.

[0115] FIG20 is a schematic diagram of a battery pack according to an embodiment of the present application.

[0116] FIG21 is an exploded view of the battery pack shown in FIG20 according to an embodiment of the present application.

[0117] FIG22 is a schematic diagram of an electrical device using a solid-state battery as a power source according to an embodiment of the present application.

[0118] FIG23 is an X-ray diffraction (XRD) diagram of the YBaCo4O7 oxygen storage material used in one embodiment of the present application, where the horizontal axis "angle" corresponds to 2θ (°).

[0119] FIG24 is a transmission electron microscope (TEM) image of coated positive electrode active particles provided in one embodiment of the present application, wherein the positive electrode active body is NCM 811 , the thickness of the oxygen storage layer shown in the figure is about 2nm.

[0120] Description of reference numerals:

[0121] 80, coated particles; 82, particle body; 84, oxygen storage layer; 842, oxygen storage material; 810, coated electrolyte particles; 812, solid electrolyte body; 820, coated positive electrode active particles; 822, positive electrode active body; 910, sulfide-based electrolyte without oxygen storage layer; 920, positive electrode active particles without oxygen storage layer; 200, positive electrode layer; 20, positive electrode film; 210, positive electrode current collector; 220, positive electrode active material layer; 220a, positive electrode active material layer including coated electrolyte particles; 220b, positive electrode active material layer including coated positive electrode active particles; 220c, positive electrode active material layer including coated electrolyte particles and coated positive electrode active particles; 220d, including A positive electrode active material layer coating positive electrode active particles and a sulfide-based electrolyte without an oxygen storage layer; 220e, a positive electrode active material layer comprising electrolyte particles coating and positive electrode active particles without an oxygen storage layer; 100, a solid electrolyte layer; 100a, a solid electrolyte layer comprising electrolyte particles coating; 100b, a solid electrolyte layer comprising a sulfide-based electrolyte without an oxygen storage layer; 10, a solid electrolyte membrane; 10a, a solid electrolyte membrane comprising electrolyte particles coating; 10b, a solid electrolyte membrane comprising a sulfide-based electrolyte without an oxygen storage layer; 300, a negative electrode layer; 1, a battery pack; 2, an upper case; 3, a lower case; 4, a battery module; 5, a solid-state battery cell; 51, a casing; 52, a solid-state battery cell; 53, a cover plate; 6, an electrical device.

[0122] It can be understood that in each figure, the solid-state battery cell 52, the positive electrode film 20, the positive electrode current collector 210, the positive electrode active material layer 220, the positive electrode layer 200, the positive electrode active material layer 220a including the coated electrolyte particles, the positive electrode active material layer 220b including the coated positive electrode active particles, the positive electrode active material layer 220c including the coated electrolyte particles and the coated positive electrode active particles, 220d including the coated positive electrode active particles and the sulfide-based electrolyte without the oxygen storage layer, the positive electrode active material layer 220e including the coated electrolyte particles and the positive electrode active particles without the oxygen storage layer, the solid electrolyte layer 100, the solid electrolyte layer 100a including the coated electrolyte particles, the solid electrolyte layer 100b including the sulfide-based electrolyte without the oxygen storage layer, the solid electrolyte layer 100c including the coated electrolyte particles ... The drawn sizes of structures such as the electrolyte membrane 10, the solid electrolyte membrane 10a including coated electrolyte particles, the solid electrolyte membrane 10b including a sulfide-based electrolyte without an oxygen storage layer, and the negative electrode layer 300 do not represent the actual sizes; the shapes and sizes of the coated particles 80, particle body 82, oxygen storage layer 84, oxygen storage material 842, coated electrolyte particles 810, solid electrolyte body 812, coated positive electrode active particles 820, positive electrode active body 822, sulfide-based electrolyte without an oxygen storage layer 910, positive electrode active particles without an oxygen storage layer 920, and other substances or local structures of the substances involved in the various drawings do not represent or are not used to limit the shapes and sizes of the actual substances, and the numbers shown in the drawings do not represent or are not used to limit the actual numbers and quantity ratios. DETAILED DESCRIPTION

[0123] Below, some embodiments of the solid-state battery materials, positive electrode active material layers, positive electrode films, solid electrolyte membranes, solid-state batteries, electrical devices and applications of the present application are described in detail with appropriate reference to the accompanying drawings. However, there may be cases where unnecessary detailed descriptions are omitted. For example, there are cases where detailed descriptions of well-known matters and repeated descriptions of actually the same structures are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate the understanding of those skilled in the art. In addition, the drawings and the following description are provided for those skilled in the art to fully understand the present application and are not intended to limit the subject matter described in the claims.

[0124] " scope " disclosed in the present application can be limited in the form of lower limit and upper limit, and given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of special range. The scope limited in this way can be to include end value or not include end value, and any end value can be included or not included independently, and can be arbitrarily combined, that is, any lower limit can form a scope with any upper limit combination. For example, if the scope of 60-120 and 80-110 is listed for specific parameters, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if minimum range values ​​1 and 2 are listed, and if maximum range values ​​3,4 and 5 are also listed, then the following scope can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise specified, numerical range " ab " represents the abbreviation of any real number combination between a and b, wherein a and b are all real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" are listed herein, and "0-5" is merely an abbreviation for these numerical combinations. Furthermore, when a parameter is expressed as an integer ≥ 2, this is equivalent to listing the parameter as, for example, the integers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, and so on. For example, when a parameter is expressed as an integer selected from "2-10", this is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0125] In this application, unless otherwise specified, "about" means within a reasonable range above or below the number. The fluctuation range may vary depending on the type and value of the number. For example, a range of ±10%, ±5%, ±2%, ±1%, etc. may be allowed. For example, taking "about 20°C" and its approximate value of ±1°C as an example, approximate values ​​such as 19°C and 19.5°C within the approximate range of "about 20°C" should also be included in the range indicated by "about 20°C".

[0126] In this application, references to "multiple," "multiple," "multiple," "several," and the like, unless otherwise specified, refer to a quantity greater than or equal to two. For example, "one or more" means one or ≥ (greater than or equal to) two. It is understood that references to "any number" of items refer to any suitable combination of multiple items, i.e., any combination of "any number" of items that is not in conflict and that enables the implementation of this application.

[0127] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0128] References to "embodiments" herein mean that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment or implementation of the present application. The appearance of such phrases in various locations in the specification does not necessarily refer to the same embodiment, nor does it necessarily refer to independent or alternative embodiments that are mutually exclusive with other embodiments. It is understood, both explicitly and implicitly, by those skilled in the art that the embodiments described herein may be combined with other embodiments. References to "implementations" herein have a similar understanding.

[0129] Those skilled in the art will appreciate that, in the methods of each embodiment or embodiment, the order in which each step is written does not mean a strict order of execution and constitutes any limitation to the implementation process, and the detailed order of execution of each step should be determined by its function and possible inherent logic. Unless otherwise specified, all steps of the present application can be performed in sequence, or can be performed randomly, or can preferably be performed in sequence. For example, method M includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed in sequence, or steps (b) and (a) performed in sequence. For example, method M may also include step (c), indicating that step (c) can be added to method M in any order, for example, method M may include steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.

[0130] In this application, open-ended technical features or technical solutions described with words such as "contain," "include," and "includes" do not exclude additional members beyond the listed members, unless otherwise specified. These technical features or solutions may be considered to provide both closed-ended features or solutions consisting of the listed members and open-ended features or solutions that include additional members beyond the listed members. For example, if A includes a1, a2, and a3, and unless otherwise specified, it may or may not include additional members, this may be considered to provide both the feature or solution "A consists of a1, a2, and a3" or "A is selected from a1, a2, and a3," and the feature or solution "A includes not only a1, a2, and a3, but also other members."

[0131] In this application, unless otherwise specified, A (such as B) means that B is a non-limiting example of A, and it can be understood that A is not limited to B.

[0132] In this application, "optionally," "optional," and "optional" mean optional, that is, they refer to either option selected from the two parallel options of "yes" or "no." If multiple "options" appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "optional" is independent. Unless otherwise specified, the descriptions "optionally include," "optionally include," etc. in this application, using "optionally include" as an example, mean "may include or not include."

[0133] In this application, unless otherwise specified, the features or solutions corresponding to "and / or" include any one of two or more relevant listed items, and also include any and all combinations of the relevant listed items, wherein any and all combinations include any two relevant listed items, any more relevant listed items, or a combination of all relevant listed items. For example, "A and / or B" means a group consisting of A, B, and "a combination of A and B." Among them, "including A and / or B" can mean "including A, including B, and including A and B", and can also mean "including A, including B, or including A and B", which can be appropriately understood according to the sentence in which it is used.

[0134] As used herein, "combination thereof", "any combination thereof", "any combination thereof" and the like include all suitable combinations of any two or more of the listed items.

[0135] Herein, the word “suitable” in “suitable combination”, “suitable method”, “any suitable method”, etc., shall be based on the technical solution that can implement the present application.

[0136] Herein, the terms "preferred," "better," "more preferable," "suitable," "comparatively better," and "preferable" are used solely to describe preferred implementations or examples and should not be construed as limiting the scope of protection of this application. If multiple "preferred" terms appear in a technical solution, each "preferred" term is considered independent unless otherwise specified and there are no contradictions or mutual constraints.

[0137] In this application, "further", "further", "particularly", "for example", "such as", "example", "for example", etc. are used for descriptive purposes to indicate differences in content, but should not be understood as limiting the scope of protection of this application.

[0138] In this application, in “the first aspect”, “the second aspect”, “the third aspect”, “the fourth aspect”, “the fifth aspect”, “the sixth aspect”, “the seventh aspect”, etc., the terms “first”, “second”, “third”, “fourth”, “fifth”, “sixth”, “seventh”, etc. are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the indicated technical features. Moreover, “first”, “second”, “third”, “fourth”, “fifth”, “sixth”, “seventh”, etc. only serve the purpose of non-exhaustive enumeration and description, and it should be understood that they do not constitute a closed limitation on quantity.

[0139] In this application, unless otherwise expressly specified or limited, a first feature being "above" or "below" a second feature may mean that the first and second features are in direct contact, or that the first and second features are in indirect contact through an intermediary. In this application, unless otherwise expressly specified or limited, a first feature being "above" or "below" a second feature may refer to a relative horizontal positional relationship, or may simply refer to an attachment relationship without limiting the relative horizontal positional relationship.

[0140] In this application, the term "room temperature" generally refers to 4°C to 35°C, and may refer to 20°C ± 5°C. In some embodiments or examples of this application, room temperature refers to 20°C to 30°C.

[0141] In this application, when referring to a data range, if the unit is followed only by the right endpoint, it means that the units of the left and right endpoints are the same. For example, "3~5h" or "3-5h" both mean that the units of the left endpoint "3" and the right endpoint "5" are both hours, and both have the same meaning as "3h~5h". Similarly, descriptions of other parameters such as temperature and size are to be understood in the same manner.

[0142] The weight or mass of the relevant components mentioned in the embodiments or examples of the present application can not only refer to the content of each component, but also represent the proportional relationship of weight or mass between each component. Therefore, as long as the content of the relevant components in accordance with the embodiments or examples of the present application is proportionally enlarged or reduced, it is within the scope described in the present application. Further, the mass involved in the embodiments or examples of the present application can be mass units known to the chemical industry such as micrograms (μg), milligrams (mg), grams (g), kilograms (kg). Unless otherwise specified, the mass ratio is equal to the corresponding weight ratio, such as the mass of substance A is m1 and the weight is W1, the mass of substance B is m2 and the weight is W2, then the mass ratio m1 / m2 of the two is numerically equal to the corresponding weight ratio W1 / W2.

[0143] In this application, unless otherwise specified, wt% represents weight percentage by weight and is numerically equivalent to the corresponding mass percentage by mass. In this application, when a weight percentage is represented by "0", it has the same meaning as "0wt%" and can be used interchangeably.

[0144] The units of parameters involved in this application, unless otherwise specified, are nm for nanometers, μm for micrometers, S / cm for Siemens per centimeter, V for volts, mPa·S for millipascals per second, and mg / cm 2 Expressed in milligrams per square centimeter, g / cm 2 Indicates grams per square centimeter, g / cm 3 represents grams per cubic centimeter, ℃ represents degrees Celsius, mA / g represents milliampere per gram, and mAh / g represents milliampere-hour per gram.

[0145] In this application, "greater than or equal to", "greater than or equal to", and "≥" have the same meaning and can be used interchangeably; "less than or equal to", "less than or equal to", and "≤" have the same meaning and can be used interchangeably; "greater than" can be equivalently expressed as ">", and "less than" can be equivalently expressed as "<". In this application, unless otherwise specified, "greater than or equal to" and "≥" can be regarded as providing two solutions of "greater than" and "equal to". In this application, unless otherwise specified, "less than or equal to" and "≤" can be regarded as providing two solutions of "less than" and "equal to".

[0146] In this application, exemplary descriptions such as "in some embodiments (or examples)" and "in one embodiment (or example)" may include but are not limited to the following meanings: these solutions can be combined with other solutions in a suitable manner to form new technical solutions.

[0147] In this application, unless otherwise specified, the "solid-state battery" provided in this application refers to a battery in which the electrolyte in the battery includes a solid electrolyte; generally, a solid-state battery includes a positive electrode layer, a solid electrolyte layer and a negative electrode layer. During the charge and discharge process of the battery, active ions are embedded and released back and forth between the positive electrode layer and the negative electrode layer. The solid electrolyte layer plays the role of conducting ions between the positive electrode layer and the negative electrode layer, and can also isolate the positive electrode layer from the negative electrode layer to prevent the positive and negative electrodes from short-circuiting. Therefore, the isolation membrane in the traditional lithium-ion battery can be omitted in the solid-state battery. The solid-state battery uses a non-flammable solid electrolyte to replace the organic electrolyte in the traditional liquid lithium-ion battery, which greatly improves the safety of the battery. In addition to improving safety, solid-state batteries can better adapt to high-energy-density positive and negative electrode materials and reduce the weight of the system, which is conducive to taking into account the improvement of energy density.

[0148] In this application, unless otherwise specified, the "solid-state battery" in any embodiment or example may be a sulfide solid-state battery. Unless otherwise specified, a "sulfide solid-state battery" refers to a solid-state battery in which the electrolyte involved in the battery includes a sulfide-based solid electrolyte. For example, the sulfide-based solid electrolyte may be located in the positive electrode layer of the sulfide solid-state battery, or may be located in the solid electrolyte layer. The sulfide solid-state battery may further be an all-solid-state battery.

[0149] In this application, unless otherwise specified, "all-solid-state battery" refers to a solid-state battery in which the electrolytes in the battery are all solid electrolytes. In this case, the positive electrode layer, the negative electrode layer and the electrolyte part are all made of solid materials, and no liquid electrolyte is provided in the battery, so it can be called an "all-solid-state battery".

[0150] In this application, unless otherwise specified, a "solid-state battery" in any embodiment or example may be, but is not limited to, a sulfide all-solid-state battery. Unless otherwise specified, a "sulfide all-solid-state battery" refers to an all-solid-state battery in which the electrolyte involved in the battery includes a sulfide-based solid electrolyte. The sulfide-based solid electrolyte can be located in the positive electrode layer of the sulfide all-solid-state battery or in the solid electrolyte layer.

[0151] In this application, unless otherwise specified, "solid electrolyte" refers to an electrolyte material or substance that exists in a solid form during the storage and preparation of a solid-state battery and its components, as well as during the operation of the solid-state battery. It is understood that the solid electrolyte exists in a solid form, including but not limited to, at room temperature.

[0152] In the present application, unless otherwise specified, the electrode layer may be a positive electrode layer or a negative electrode layer, and the "active material" in the electrode layer refers to a substance that can reversibly embed and release active ions. Unless otherwise specified, "negative electrode active material" refers to a substance used in the negative electrode layer that can reversibly embed and release active ions; "positive electrode active material" refers to a substance used in the positive electrode layer that can reversibly release and embed active ions. When the solid-state battery is charging, the active ions are released from the positive electrode and embedded in the negative electrode through the solid electrolyte layer; when the solid-state battery is discharging, the active ions are released from the negative electrode and embedded in the positive electrode. There is no special limitation on the active ions. Non-restrictively, the active ions can be lithium ions, which corresponds to a lithium-ion solid-state battery.

[0153] In this application, "electrode active material", "electrode active substance", "active material" and "active substance" have the same meaning and can be used interchangeably; "positive electrode active substance" and "positive electrode active material" have the same meaning and can be used interchangeably; "negative electrode active substance" and "negative electrode active material" have the same meaning and can be used interchangeably. "Positive electrode active substance" and "positive electrode active material" have the same meaning and can be used interchangeably; "negative electrode active substance" and "negative electrode active material" have the same meaning and can be used interchangeably.

[0154] In this application, unless otherwise specified, the term "electrode active material layer" includes at least one of the positive electrode active material layer in the positive electrode layer and the negative electrode active material layer in the negative electrode layer. Depending on the specific circumstances, the electrode active material layer may refer to the positive electrode active material layer or the negative electrode active material layer. It is understood that the positive electrode active material layer contains a positive electrode active substance, and the negative electrode active material layer contains a negative electrode active substance. In this application, the term "electrode active material layer" may also be referred to as the "active material layer."

[0155] In the present application, unless otherwise specified, the positive electrode layer at least includes a positive electrode active material layer.

[0156] In the present application, unless otherwise specified, the positive electrode active material layer includes at least positive electrode active particles and generally also includes positive electrode electrolyte particles.

[0157] In this application, unless otherwise specified, “positive electrode active particles” refer to particles containing positive electrode active materials, which have the ability to reversibly release and embed active ions.

[0158] In this application, unless otherwise specified, "positive electrode electrolyte particles" and "positive electrode solid electrolyte" have the same meaning and can be used interchangeably to refer to solid electrolytes that can be used in positive electrode membranes or positive electrode layers. Positive electrode electrolyte particles can enhance the ion conductivity of the positive electrode membrane or positive electrode layer and reduce interfacial impedance, thereby promoting the charge transfer efficiency between the positive electrode active material and the outside world and fully releasing its capacity.

[0159] In this application, unless otherwise specified, “negative electrode active particles” refer to particles containing negative electrode active materials, which have the ability to reversibly embed and de-embed active ions.

[0160] In addition to using solid electrolyte materials in the solid electrolyte layer, solid electrolyte materials are also usually provided in the positive electrode layer. The current common practice for solid-state batteries is to adopt a composite positive electrode model on the positive electrode side of the solid-state battery, and to set positive electrode active materials and solid electrolytes in the positive electrode at the same time, and to use solid electrolytes to enhance the ion conductivity of the positive electrode side, promote the charge transfer efficiency between the positive electrode active material and the outside world and the full release of its capacity, and reduce impedance; at the same time, the electronic conductivity of the positive electrode active material itself is used to conduct electrons to improve the cycle stability of the battery. Among the many solid electrolyte materials, sulfide solid electrolytes have an ultra-high ionic conductivity (about 10 -3 ~10 -2 S / cm, almost the same as commercial liquid electrolytes) and good flexibility, giving it excellent ion conductivity and good deformation ability, making it a solid electrolyte material with the most practical and industrial prospects.

[0161] However, sulfide solid electrolytes have poor air stability and are sensitive to moisture and oxygen in the air. They easily release hydrogen sulfide gas when in contact with air, causing a decrease in ionic conductivity and posing certain safety risks, which seriously restricts the practical application of sulfide solid electrolytes.

[0162] On the one hand, sulfide solid electrolytes easily absorb moisture from the air and react, resulting in the production of toxic hydrogen sulfide gas, which also impairs the rapid ion conductivity of the sulfide solid electrolyte. During the preparation of solid-state batteries, the positive electrode layer and the solid electrolyte layer inevitably come into contact with moisture in the air. During the preparation and assembly of solid-state batteries, the air instability of the sulfide electrolyte causes the sulfide solid electrolyte in the positive electrode layer and the solid electrolyte layer to decompose, resulting in impaired ion conductivity. This will increase the interfacial impedance between the positive electrode active particles and the positive electrode electrolyte particles in the positive electrode layer, and between the positive electrode layer and the solid electrolyte layer, affecting the electrochemical performance of the prepared solid-state battery and damaging the battery's cycle performance.

[0163] On the other hand, sulfide solid electrolytes also have the disadvantage of being easily oxidized and decomposed. Oxygen in the air and oxygen that may be released from the positive electrode layer during battery operation will also attack the sulfide solid electrolyte, which may cause oxidative decomposition of the sulfide electrolyte, thereby reducing the rapid ion conductivity of the sulfide solid electrolyte, increasing the interface impedance inside the positive electrode layer and between the positive electrode layer and the solid electrolyte layer, deteriorating the electrochemical properties of the prepared solid-state battery, and damaging the battery's cycle performance.

[0164] Based on this, according to various embodiments and examples of the present application, the embodiments and examples of the present application provide at least solid-state battery materials, positive electrode active material layers, positive electrode films, solid electrolyte membranes, solid-state batteries, electrical devices, and applications. Using this solid-state battery material as a raw material can improve the discharge capacity and cycle performance of sulfide solid-state batteries.

[0165] In a first aspect of the present application, a solid-state battery material is provided, comprising a coated particle, the coated particle comprising a particle body and an oxygen storage layer located at at least a portion of a surface of the particle body, the oxygen storage layer comprising an oxygen storage material;

[0166] Wherein, the coated particles are at least one of coated positive electrode active particles and coated electrolyte particles;

[0167] When the coated particles are coated positive electrode active particles, the particle body is a positive electrode active body, and the positive electrode active body contains a positive electrode active material;

[0168] When the coated particles are coated electrolyte particles, the particle body is a solid electrolyte body, and the solid electrolyte body contains a sulfide electrolyte.

[0169] In this application, unless otherwise specified, "solid-state battery material" refers to a material that can be used in solid-state batteries, but is not limited to such applications. Unless otherwise specified, the solid-state battery material does not contain liquid electrolytes except for the coated particles.

[0170] In some embodiments, the solid-state battery material may be a sulfide solid-state battery material. Unless otherwise specified, a "sulfide solid-state battery material" is a material that can be used in sulfide solid-state batteries, but is not limited to such applications. Unless otherwise specified, the sulfide solid-state battery material includes a sulfide-based solid electrolyte. For example, when the sulfide solid-state battery material includes coated electrolyte particles, the coated electrolyte particles themselves are a sulfide-based solid electrolyte; for another example, when the sulfide solid-state battery material includes coated positive electrode active particles, the sulfide solid-state battery material also includes a sulfide-based electrolyte.

[0171] For example, the sulfide solid-state battery material can further be an all-solid-state battery material. Unless otherwise specified, "all-solid-state battery material" refers to a material that can be used in all-solid-state batteries, but is not limited to such applications. Unless otherwise specified, all-solid-state battery materials do not include liquid electrolytes.

[0172] In some embodiments, the solid-state battery material can be a sulfide all-solid-state battery material. Unless otherwise specified, a "sulfide all-solid-state battery material" is a material that can be applied to a sulfide all-solid-state battery, but is not limited to this application. Unless otherwise specified, the sulfide all-solid-state battery material includes a sulfide-based solid electrolyte and no liquid electrolyte is provided. For example, when the sulfide all-solid-state battery material includes coated electrolyte particles, the coated electrolyte particles are a sulfide-based solid electrolyte; for another example, when the sulfide all-solid-state battery material includes coated positive electrode active particles, the sulfide all-solid-state battery material also includes a sulfide-based electrolyte.

[0173] In this application, unless otherwise specified, the "solid-state battery" involved in the implementation methods or examples of this application may be a sulfide solid-state battery.

[0174] In some embodiments, a "sulfide solid-state battery" comprises a sulfide-based electrolyte in at least one of the solid electrolyte layer and the positive electrode active material layer.

[0175] In this application, unless otherwise specified, "sulfide electrolyte", "sulfide electrolyte component" and "sulfide solid electrolyte component" have the same meaning and can be used interchangeably, referring to a solid electrolyte component in the form of sulfide, wherein the sulfide electrolyte includes sulfur (S) element in the form of sulfide. The existence form of the "sulfide electrolyte" involved in the embodiments or examples of the present application is not particularly limited, and it can be an independent sulfide electrolyte substance or a part of a composite material, such as a sulfide electrolyte component located inside the coated electrolyte particles (in this case, the solid electrolyte body coating the electrolyte particles contains a sulfide electrolyte). The "sulfide electrolyte" involved in the embodiments or examples of the present application can be in either the solid electrolyte layer or the positive electrode layer, can be contained in the positive electrode electrolyte particles, or can be contained in the electrolyte substance of the solid electrolyte layer.

[0176] In this application, unless otherwise specified, "sulfide-based electrolyte," "sulfide-based solid electrolyte," and "sulfide-based electrolyte particles" have the same meaning and can be used interchangeably. They refer to a solid electrolyte containing a sulfide electrolyte component, which can be the sulfide electrolyte itself, or a coating layer provided on the surface of the sulfide electrolyte, but is not limited thereto. The coating layer provided on the surface of the sulfide electrolyte can be an oxygen storage layer, but is not limited thereto. Without limitation, the sulfide-based electrolyte provided with a coating layer can be the coated electrolyte particles involved in the embodiments or examples of this application.

[0177] In this application, unless otherwise specified, the types of sulfide electrolyte components contained in different locations or materials of a "sulfide solid-state battery" can be the same or different. For example, the types of sulfide electrolyte components contained in the positive electrode layer and the solid electrolyte layer can be the same or different. The types of sulfide electrolyte components in the coated electrolyte particles and the sulfide-based electrolyte without an oxygen storage layer can also be the same or different.

[0178] In this application, unless otherwise specified, a "coated particle" is a solid object comprising a particle body and an oxygen storage layer located on at least a portion of the particle body's surface. The oxygen storage layer may be located on a portion of the particle body's surface or may completely coat the particle body. In some embodiments, the coated particle comprises a particle body and an oxygen storage layer located on a portion of the particle body's surface.

[0179] In this application, unless otherwise specified, "oxygen storage layer" refers to a layer containing oxygen storage material, which may be continuous or discontinuous. For example, the oxygen storage layer may be continuously or discontinuously distributed on the surface of the particle body.

[0180] In this application, unless otherwise specified, "oxygen storage material" refers to a material capable of absorbing and storing oxygen molecules or atoms. Unless otherwise specified, the oxygen storage material referred to in this application, after absorbing and storing oxygen, is capable of substantially maintaining the ability to retain the absorbed oxygen during the storage and preparation of solid-state batteries and components comprising such batteries, with substantially no reversible release of oxygen.

[0181] In this application, unless otherwise specified, "particle body" refers to the internal solid portion of the coated particle that is coated by the oxygen storage layer. Unless otherwise specified, the "particle body" itself does not contain oxygen storage material. The structure and shape of the particle body are not particularly limited. The particle body itself may or may not have a coating layer. It is understood that the coating layer of the particle body itself does not contain oxygen storage material. As a non-limiting example, the positive electrode active body in the coated positive electrode active particle may include a coating layer.

[0182] In this application, unless otherwise specified, “located on at least a portion of the surface of the X solid” means located on at least a portion of the surface of the X solid.

[0183] This solid-state battery material can be used as a sulfide solid-state battery material, comprising coated particles provided with a surface oxygen storage layer, wherein the oxygen storage layer is located on at least a portion of the surface of the coated particles; the coated particles can be positive electrode active particles coated with a surface oxygen storage layer, or can be sulfide-based electrolyte particles coated with a surface oxygen storage layer, or can be a combination of the two coated particles coated with a surface oxygen storage layer. When using this solid-state battery material to prepare a sulfide solid-state battery, the oxygen storage material in the oxygen storage layer absorbs oxygen, which can reduce the contact probability between the sulfide electrolyte and oxygen, thereby improving the chemical stability of the sulfide electrolyte during the battery preparation process, facilitating full utilization of the sulfide electrolyte's rapid ion conduction function, thereby promoting stable operation of the solid-state battery and improving the discharge capacity and cycle performance of the sulfide solid-state battery.

[0184] It should be noted that any one of the solid-state battery materials, sulfide solid battery materials or sulfide all-solid-state battery materials described in this application can be directly introduced into the preparation process of the solid-state battery, sulfide battery or sulfide all-solid-state battery in solid form by a dry method, or can be introduced into the battery preparation process in the form of a slurry by a wet method, and then the solvent is removed by a subsequent drying process, leaving only the solid material in the solid-state battery material, sulfide solid battery material or sulfide all-solid-state battery material in the battery.

[0185] In some embodiments, the solid-state battery material is a solid material whose constituent materials are all solid.

[0186] In some embodiments, the solid-state battery material is a slurry composed of a solid material and a dispersion solvent. It is understood that the solid material in the slurry includes at least the aforementioned coated particles. Typically, the dispersion solvent is a non-aqueous solvent. As non-limiting examples, the removable solvent may include one or more of p-xylene, trimethylbenzene, butyl butyrate, heptane, and the like, and may further include p-xylene.

[0187] In some embodiments, the solid-state battery material is used to form a cathode film or a cathode layer in a solid-state battery, and can further be applied to a cathode layer or cathode film containing a sulfide electrolyte component. Without limitation, the sulfide electrolyte component can be provided by coated electrolyte particles in the solid-state battery material, or by cathode electrolyte particles in the form of sulfide.

[0188] In some embodiments of the present application, a coated electrolyte particle is provided. The coated electrolyte particle is a coated particle in the present application, wherein the particle body is a solid electrolyte body, and the solid electrolyte body contains a sulfide electrolyte.

[0189] In this application, unless otherwise specified, "coated electrolyte particles" include a solid electrolyte body and an oxygen storage layer located on at least a portion of the surface of the solid electrolyte body, wherein the solid electrolyte body comprises a sulfide electrolyte, and the oxygen storage layer comprises an oxygen storage material. Thus, coated electrolyte particles are sulfide-based electrolyte particles having an oxygen storage layer disposed on their surface. Without limitation, coated electrolyte particles can be obtained by coating a sulfide-based electrolyte (e.g., sulfide electrolyte particles) without an oxygen storage layer with an oxygen storage material.

[0190] The coated electrolyte particles can be used as a solid electrolyte in the solid electrolyte layer of a solid-state battery, or as a solid electrolyte in an electrode active material layer (i.e., as a positive electrode electrolyte particle), for example, as a solid electrolyte in a positive electrode active material layer. When the coated electrolyte particles are used to prepare a separate solid electrolyte membrane or positive electrode membrane, or when a positive electrode layer is formed on a base membrane (such as a solid electrolyte membrane), and in the process of preparing a solid-state battery using a membrane sheet containing the coated electrolyte particles, the oxygen storage layer provided on the surface of the coated electrolyte particles can protect the sulfide electrolyte, reduce or isolate the decomposition effect of oxygen in the air on the sulfide electrolyte, thereby improving the chemical stability of the sulfide electrolyte during the battery preparation process, and helping the sulfide electrolyte to fully exert its fast ion conduction function, promote the stable operation of the solid-state battery, and improve the discharge capacity and cycle performance of the sulfide solid-state battery. In addition, the oxygen storage layer provided on the surface of the coated electrolyte particles can also reduce or isolate the direct contact between the sulfide electrolyte and moisture in the air, inhibit the decomposition of the sulfide electrolyte and the generation of hydrogen sulfide gas, and help improve the chemical stability of the sulfide electrolyte. It can be seen that by setting an oxygen storage layer on the surface of the sulfide electrolyte, the oxygen storage material in the oxygen storage layer can absorb and store oxygen. In addition, it can also block the direct contact between the sulfide electrolyte and moisture, thereby giving the coated electrolyte particles better air stability.

[0191] In some embodiments of the present application, a coated positive electrode active particle is provided. The coated positive electrode active particle is another type of coated particle in the present application, wherein the particle body is a positive electrode active body, and the positive electrode active body contains a positive electrode active material.

[0192] In this application, unless otherwise specified, "coated positive electrode active particles" include a positive electrode active body and an oxygen storage layer located on at least a portion of the surface of the positive electrode active body. The positive electrode active body includes a positive electrode active material, and the oxygen storage layer includes an oxygen storage material. Thus, coated positive electrode active particles are positive electrode active particles having an oxygen storage layer disposed on their surface. Without limitation, coated electrolyte particles can be obtained by coating positive electrode active particles without an oxygen storage layer with an oxygen storage material.

[0193] The coated positive electrode active particles can provide positive electrode active materials in the positive electrode layer of the solid-state battery, that is, they can be used as positive electrode active particles. For solid-state batteries, generally, positive electrode electrolyte particles are arranged in the positive electrode active material layer of the positive electrode layer to play the role of accelerating ion conduction, reducing interface impedance, and giving full play to the capacity of the positive electrode active particles. When the positive electrode electrolyte particles are sulfide-based electrolytes, that is, containing sulfide electrolytes, during the preparation of the positive electrode film, the positive electrode layer of the solid-state battery, and the preparation of the solid-state battery, the oxygen storage layer arranged on the surface of the coated positive electrode active particles can absorb and store oxygen, which can reduce or isolate the attack and decomposition of oxygen in the air on the sulfide electrolyte, thereby improving the chemical stability of the sulfide electrolyte during the battery preparation process, which is conducive to the sulfide electrolyte giving full play to its role of rapid ion conduction, reducing interface resistance, promoting the stable operation of the solid-state battery, and improving the discharge capacity and cycle performance of the sulfide solid-state battery. In addition, it can also improve the rate performance of the solid-state battery. It can be seen that by providing an oxygen storage layer on the surface of the positive electrode active material, it can also play a role in protecting the sulfide-based electrolyte mixed with it, thereby improving the air stability of the positive electrode electrolyte particles and the positive electrode layer, which is beneficial to improving the aforementioned electrochemical properties of the solid-state battery.

[0194] The oxygen storage materials involved in the embodiments or examples of the present application can be oxygen storage materials known in the art.

[0195] In some embodiments, the oxygen storage material is a "chemical oxygen storage material" that absorbs and fixes oxygen through a chemical reaction with oxygen.

[0196] Without limitation, the oxygen storage material may include one or more of lanthanide metal oxysulfate type oxygen storage materials, yttrium barium cobalt oxide type oxygen storage materials and perovskite type oxygen storage materials. These oxygen storage materials can absorb and fix oxygen (O) by storing it in the lattice of the oxygen storage material. 7+δ Taking (YBCO) oxygen storage material as an example, the stoichiometric ratio of its oxygen (O) element can change within a certain range, storing oxygen molecules or oxygen atoms in the lattice of the oxygen storage material, thereby absorbing and fixing oxygen, and its oxygen storage capacity is very high, which can reach 2700μmol O / g. As a non-limiting example, the absorption and fixation of oxygen by lanthanide metal sulfate-type oxygen storage materials, yttrium barium cobalt oxide-type oxygen storage materials and perovskite-type oxygen storage materials are relatively stable, and reversible release of oxygen will not occur during the storage and process involved in solid-state batteries and their components. Taking YBaCo4O 7+δ For example, oxygen re-release may occur when heated to extremely high temperatures above 200°C.

[0197] Without limitation, the lanthanide metal oxysulfate type oxygen storage material may include a material having the chemical formula Ln2O2SO4-δ1 An oxygen storage material, wherein Ln is a lanthanide metal element, which may include but is not limited to one or more elements selected from La, Ce, Pr, Nd, Sm, Eu, Gd, and Tb, and 0≤δ1≤4. Without limitation, δ1 can be any of the following values ​​or an interval consisting of any two of the following values: 0, 0.01, 0.02, 0.04, 0.05, 0.06, 0.08, 0.1, 0.2, 0.4, 0.5, 0.6, 0.8, 1, 1.2, 1.5, 2, 2.5, 3, 3.5, 3.6, 3.8, 3.9, 3.92, 3.94, 3.95, 3.96, 3.98, 3.99, etc. δ1 can also be selected from the following ranges: 0<δ1<4, 0≤δ1<4, etc.

[0198] Without limitation, the yttrium barium cobalt oxide type oxygen storage material may include a chemical formula (Y x M1 (1-x) )(Ba y M2 (1-y) )(Co z M3 (1-z) )4O 7+δ2 An oxygen storage material, wherein M1 can be selected from, but not limited to, one or more elements selected from Ca, In, Dy, Ho, Er, Tm, Yb, and Lu, M2 is Sr, and M3 can be selected from, but not limited to, one or more elements selected from Mn, Fe, Ni, Cu, Zn, Al, Ga, and Zr, 0≤x≤1, 0≤y≤1, 0≤z≤1, and 0≤δ2≤1.5. Without limitation, x, y, and z can each independently be any of the following values ​​or an interval consisting of any two of the following values: 0, 0.01, 0.02, 0.04, 0.05, 0.06, 0.08, 0.1, 0.2, 0.4, 0.5, 0.6, 0.8, 0.9, 0.92, 0.94, 0.95, 0.96, 0.98, 0.99, 1, etc. Without limitation, δ2 can be any of the following values ​​or an interval consisting of any two of the following values: 0, 0.01, 0.02, 0.04, 0.05, 0.06, 0.08, 0.1, 0.2, 0.4, 0.5, 0.6, 0.8, 1, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.42, 1.44, 1.45, 1.46, 1.48, 1.49, 1.5, etc.

[0199] Without limitation, the perovskite oxygen storage material may include a material having the chemical formula La 1-a A a Mn 1-b B b O 3-δ3An oxygen storage material, wherein A is selected from one or more elements of Sr, Y, Ce, Pr, and Nd, and B is selected from one or more elements of Ni, Fe, Cu, and Co, and 0≤a≤1, 0≤b≤1, and 0≤δ3≤1. Without limitation, a and b can each independently be any of the following values ​​or an interval consisting of any two of the following values: 0, 0.01, 0.02, 0.04, 0.05, 0.06, 0.08, 0.1, 0.2, 0.4, 0.5, 0.6, 0.8, 0.9, 0.92, 0.94, 0.95, 0.96, 0.98, 0.99, 1, etc. Without limitation, δ3 can be any of the following values ​​or an interval consisting of any two of the following values: 0, 0.01, 0.02, 0.04, 0.05, 0.06, 0.08, 0.1, 0.2, 0.4, 0.5, 0.6, 0.8, 0.9, 0.92, 0.94, 0.95, 0.96, 0.98, 0.99, 1, etc.

[0200] In some embodiments, the oxygen storage material may include La2O2SO4, YBaCo4O7, La 0.8 Sr 0.2 CoO3, Ce 0.6 Zr 0.3 Al 0.1 O 1.95 One or more of the following.

[0201] In some embodiments, the weight proportion of the oxygen storage material in the coated particles (such as coated positive electrode active particles or coated electrolyte particles) can be 0.1wt% to 10wt%, optionally 0.5wt% to 5wt%, or any of the following percentages or an interval consisting of any two of the following percentages: 0.1wt%, 0.2wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.8wt%, 1wt%, 1.2wt%, 1.5wt%, 1.6wt%, 1.8wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, 8wt%, 9wt%, 10wt%, etc. The coated particles can be coated positive electrode active particles or coated electrolyte particles.

[0202] In some embodiments, the thickness of the oxygen storage layer is 0.1 nm to 50 nm, optionally 0.5 nm to 10 nm, and may also be any of the following thicknesses or a range consisting of any two of the following thicknesses: 0.1 nm, 0.2 nm, 0.4 nm, 0.5 nm, 0.6 nm, 0.8 nm, 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 8 nm, 10 nm, 12 nm, 15 nm, 16 nm, 18 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, etc. The oxygen storage layer may be an oxygen storage layer coating the positive electrode active particles or an oxygen storage layer coating the electrolyte particles.

[0203] In some embodiments, the coated particles meet one or more of the following characteristics (any numerical parameter in the following characteristics can also be selected from any suitable value or range in the context):

[0204] The weight proportion of the oxygen storage material in the coated particles (such as coated positive electrode active particles or coated electrolyte particles) is 0.1wt% to 10wt%, and can be optionally 0.5wt% to 5wt%;

[0205] The thickness of the oxygen storage layer is 0.1 nm to 50 nm, and can be optionally 0.5 nm to 10 nm.

[0206] By controlling either the weight percentage of the oxygen storage material in the coated particles or the thickness of the oxygen storage layer, the amount of oxygen storage material coated can be adjusted. It is understood that adjusting both parameters simultaneously can also adjust the amount of oxygen storage material coated. By controlling at least one of the weight percentage of the oxygen storage material in the coated particles and the thickness of the oxygen storage layer within the aforementioned range, not only is it beneficial to improve the stability of the sulfide electrolyte components involved in the solid-state battery preparation process, but it also helps the sulfide electrolyte fully utilize its rapid ion conductivity.

[0207] According to the stoichiometric ratio of the oxygen storage material described in this application, an oxygen storage material with a target chemical composition can be prepared by selecting a suitable precursor material using, but not limited to, existing methods in the art.

[0208] In some embodiments, the required precursor material, solvent and optional auxiliary agent can be mixed according to the stoichiometric ratio of the oxygen storage material, uniformly dispersed, ball-milled, dried, sintered for the first time, ground to a suitable particle size (such as 1nm to 100nm), and optionally sintered for a second time to prepare the required oxygen storage material.

[0209] Taking the preparation of YBaCo4O7 (which can be denoted as YBCO) oxygen storage material as an example, the precursor materials can be Y2O3, BaCO3 and Co3O4, the solvent can be an organic solvent (such as ethanol), no other additives are required, it can be dried at 80°C to dry (a forced air drying oven can be used), the atmosphere for the first sintering treatment can be air, the first sintering treatment can be carried out at 1000°C for 12 hours, the atmosphere for the second sintering treatment can be air, and the second sintering treatment can be carried out at 1100°C for 24 hours.

[0210] Taking the preparation of YBaCo4O7 oxygen storage material as an example, the precursor materials can be Y2O3, BaCO3 and Co3O4, the solvent can be an organic solvent (such as ethanol), no other additives are required, it can be dried at 80°C to dry (a forced air drying oven can be used), the atmosphere for the first sintering treatment can be air, the first sintering treatment can be carried out at 1000°C for 12 hours, the atmosphere for the second sintering treatment can be air, and the second sintering treatment can be carried out at 1100°C for 24 hours.

[0211] In some embodiments, the required precursor material, solvent and optional auxiliary agent can be mixed according to the stoichiometric ratio of the oxygen storage material to form a composite solution, and the reaction is carried out under continuous dispersion and heating conditions. During the reaction, the pH value of the reaction system can be adjusted by the pH adjuster to generate an intermediate precipitate, solid-liquid separation (such as filtration), washing to neutrality, drying, a first sintering treatment, grinding to a suitable particle size (such as 1nm to 100nm), and optionally a second sintering treatment to prepare the required oxygen storage material.

[0212] Taking the preparation of La2O2SO4 oxygen storage material as an example, the precursor materials can be La(NO3)3·6H2O and sodium dodecylsulfonate CH3(CH2) 10 CH2SO3Na, the auxiliary agent can be ammonia water, the continuous dispersion condition can be continuous stirring, the heating condition can be heating at 40°C for 1 hour and then heating to 50°C and stirring for 10 hours, the pH of the reaction system can be 9, the atmosphere for the first sintering treatment can be air, the first sintering treatment can be carried out at 550°C for 5 hours, and La2O2SO4 oxygen storage material can be obtained after grinding.

[0213] To prepare La 0.8 Sr 0.2 Taking CoO3 oxygen storage material as an example, the precursor materials can be La(NO3)3·6H2O, Co(NO3)2·6H2O and Sr(NO3)2, and the auxiliary agent can be urea. The amount of urea is the same as that of La 0.8 Sr 0.2The molar ratio of the theoretical yield of CoO3 can be 1:(3-5), such as 1:4. The reaction can be carried out under continuous stirring and heating at 80°C. The pH regulator can be ammonia water. The pH value of the reaction system can be 9. The atmosphere for the first sintering treatment can be air. The first sintering treatment can be carried out at 700°C for 5 hours. The atmosphere for the second sintering treatment can be air. The second sintering treatment can be carried out at 1050°C for 10 hours.

[0214] To prepare Ce 0.6 Zr 0.3 Al 0.1 O 1.95 For example, the oxygen storage material can be cerium nitrate, zirconium nitrate and aluminum nitrate, the solvent can be water, and the auxiliary agent can be urea. The amount of urea is the same as that of Ce. 0.6 Zr 0.3 Al 0.1 O 1.95 The molar ratio of the theoretical yield can be 1:(3-5), such as 1:4. The reaction can be carried out under continuous stirring and heating at 80°C. The pH adjuster can be ammonia water. The pH value of the reaction system can be 9. The atmosphere for the first sintering treatment can be air. The first sintering treatment can be carried out at 500°C for 5 hours. The atmosphere for the second sintering treatment can be air. The second sintering treatment can be carried out at 1000°C for 10 hours.

[0215] For those skilled in the art, according to the structure and chemical composition of the coating material described in this application, it can be prepared by using methods including but not limited to existing particle coating methods. As a non-limiting example, such as physical coating methods. The solid oxygen storage material can be coated onto at least a portion of the surface of the particle body (such as the positive electrode active body or the solid electrolyte body containing a sulfide electrolyte) using existing physical coating methods. Dry coating can be used, but is not limited to this. Please also refer to the examples below. As otherwise noted, the oxygen storage material can be coated on at least a portion of the surface of the particle body in an inert atmosphere (such as an argon atmosphere).

[0216] In some embodiments, an oxygen storage material having a suitable particle size (corresponding to oxygen storage particles) can be mixed with the particle body according to the desired coating amount and heat treated to obtain coated particles with the desired structure and chemical composition. In some embodiments, the YBCO-coated lithium transition metal oxide (such as lithium nickel cobalt manganese oxide, further such as NCM 811 ) as an example, the heat treatment temperature can be 450°C for 5 hours.

[0217] In some embodiments, the oxygen storage material with a suitable particle size (corresponding to oxygen storage particles) can be made into a glue solution, which is then fully mixed with the particle body according to the required coating amount, and then heated to obtain coated particles with the required structure and chemical composition. In some embodiments, the YBaCo4O7 coated sulfide electrolyte (such as Li 5.5 PS 4.5 Cl 1.5 ) as an example, the glue solution can be prepared in xylene, and the heating treatment method can be vacuum drying at 120℃ for 10 hours.

[0218] In some embodiments, in-situ coating can be performed on the surface of the particle body. In some embodiments, a reaction system including a precursor material of an oxygen storage material can be reacted in-situ on the surface of the particle body and the solvent can be removed. During the in-situ reaction, the pH value of the reaction system can be adjusted by a pH adjuster. After the collected solid intermediate is sintered, an oxygen storage layer can be formed on at least a portion of the surface of the particle body to obtain coated particles with an oxygen storage layer. 0.8 Sr 0.2 CoO3 coated lithium transition metal oxides (such as lithium nickel cobalt manganese oxide, further such as NCM 811 ) as an example, the precursor materials of the oxygen storage material can be La(NO3)3·6H2O, Co(NO3)2·6H2O and Sr(NO3)2, the solvent can be water, the auxiliary agent can be hexadecyltrimethylammonium bromide, the pH regulator can be ammonia water, the pH value of the reaction system can be 9, the temperature for the in-situ reaction can be 80°C, and the conditions for the sintering treatment can include heating at 500°C for 5h.

[0219] In the present application, particle structure analysis methods such as transmission electron microscopy (TEM) can be used to detect and analyze whether the coated particles have a coating layer. Elemental analysis methods such as energy dispersive spectrometer (EDS), X-ray diffraction (XRD) technology, and inductively coupled plasma spectrometer (ICP method) can also be combined to detect and identify whether the coating contains oxygen storage materials and the element types and chemical composition of the particles themselves. These methods can also be used to analyze parameters such as the thickness of the oxygen storage layer, the weight proportion or weight percentage of the oxygen storage layer in the oxygen storage material in the coated particles.

[0220] In some embodiments, the coated particle 80 includes a particle body 82 and an oxygen storage layer 84 located on the surface of the particle body 82. Please refer to FIG1 .

[0221] In some embodiments, the coated particle 80 includes a particle body 82 and an oxygen storage layer 84 located on the surface of the particle body 82. The oxygen storage layer 84 includes an oxygen storage material 842. See FIG. 2 .

[0222] In some embodiments of the present application, at least two coated particles are provided (see Figure 3), one is a coated positive electrode active particle 820, and the other is a coated electrolyte particle 810; the coated positive electrode active particle 820 includes a positive electrode active body 822 and an oxygen storage layer 84 located on the surface of the positive electrode active body 822, and the oxygen storage layer 84 includes an oxygen storage material 842; the coated electrolyte particle 810 includes a solid electrolyte body 812 and an oxygen storage layer 84 located on the surface of the solid electrolyte body 812, and the oxygen storage layer 84 includes an oxygen storage material 842.

[0223] In some embodiments, the oxygen storage material includes oxygen storage particles; the particle size of the oxygen storage particles is 1nm to 100nm, optionally 1nm to 50nm, and can also be any of the following sizes or an interval consisting of any two of the following sizes: 1nm, 10nm, 20nm, 30nm, 40nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, 100nm, etc.

[0224] In this application, unless otherwise specified, “particle size of oxygen storage particles” refers to the maximum diameter of the oxygen storage particles in each direction.

[0225] In this application, the "particle size of the oxygen storage particles" can be tested and analyzed using particle size analysis methods such as transmission electron microscopy (TEM) and laser particle size analysis. These testing methods can also be used to test and analyze the particle size of other particulate matter involved in this application (such as coated positive electrode active particles, coated electrolyte particles, positive electrode active particles, granular electrolyte materials, raw materials for providing particle bodies, etc.), such as parameters such as particle size and particle size distribution, and the average values ​​of some size parameters.

[0226] The oxygen storage material in the oxygen storage layer can be granular oxygen storage particles. In this case, the specific surface area of ​​the oxygen storage particles can be adjusted by controlling the particle size of the oxygen storage particles. Controlling the particle size within the aforementioned range helps the particles have a larger oxygen-absorbing surface area, allowing the oxygen storage material to better perform its aforementioned function of absorbing and storing oxygen, while also further facilitating its ability to isolate moisture from the air.

[0227] In some embodiments, the D coating the positive electrode active particles v50 is 0.1μm to 20μm, and can be optionally 1μm to 10μm, or can be any of the following sizes or an interval consisting of any two of the following sizes: 0.1μm, 0.2μm, 0.3μm, 0.4μm, 0.5μm, 0.6μm, 0.8μm, 1μm, 1.5μm, 2μm, 2.5μm, 3μm, 3.5μm, 4μm, 4.5μm, 5μm, 5.5μm, 6μm, 6.5μm, 7μm, 7.5μm, 8μm, 8.5μm, 9μm, 9.5μm, 10μm, 10.5μm, 11μm, 11.5μm, 12μm, 12.5μm, 13μm, 13.5μm, 14μm, 14.5μm, 15μm, 15.5μm, 16μm, 16.5μm, 17μm, 17.5μm, 18μm, 18.5μm, 19μm, 19.5μm, 20μm, etc.

[0228] In the context of this application, the volume cumulative distribution particle size D can be used v N (where N represents any value selected from 0 to 100) is used to characterize the particle size of the material, which refers to the particle size corresponding to when the cumulative volume distribution percentage of the material reaches N%. The particle size is less than or equal to D v The volume percentage of N is N%. v N can be obtained from the volume cumulative distribution curve of the material particle size. If there is no other explanation, the volume cumulative distribution curve starts from zero from the small particle size side. v 50 is used as an example. In this application, if there is no other description, D v 50 refers to the particle size corresponding to when the cumulative volume distribution percentage of the material reaches 50%. This parameter indicates that the particle size of 50% of the material volume is less than or equal to D v 50, and 50% of the volume of the material has a particle size larger than D v 50. Those skilled in the art will understand that v 50, and can be measured using instruments and methods known in the art. For example, it can be conveniently measured using a laser particle size analyzer, such as the Mastersizer 2000E laser particle size analyzer or the LS-909 laser particle size analyzer (Omega), manufactured by Malvern Instruments Ltd., UK, in accordance with GB / T 19077-2016 Particle Size Distribution by Laser Diffraction Method. Furthermore, for equipment such as the Malvern 2000 laser particle size analyzer, testing can be performed according to the standard procedure GB / T 19077-2016 / ISO 13320:2009.

[0229] In some embodiments, the particle size of the positive electrode active body is 0.1 μm to 20 μm, optionally 1 μm to 10 μm, and can also be any of the following sizes or an interval consisting of any two of the following sizes: 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.8 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm m, 6.5μm, 7μm, 7.5μm, 8μm, 8.5μm, 9μm, 9.5μm, 10μm, 10.5μm, 11μm, 11.5μm, 12μm, 12.5μm, 13μm, 13. 5μm, 14μm, 14.5μm, 15μm, 15.5μm, 16μm, 16.5μm, 17μm, 17.5μm, 18μm, 18.5μm, 19μm, 19.5μm, 20μm, etc.

[0230] In this application, unless otherwise specified, “particle size of the positive electrode active body” refers to the maximum diameter of the positive electrode active body in each direction.

[0231] In this application, the size of a part of the particles, such as "particle size of the positive electrode active body" and "particle size of the solid electrolyte body", can also be tested and analyzed using particle structure and size analysis methods such as transmission electron microscopy (TEM), and can be analyzed in combination with elemental analysis methods.

[0232] In some embodiments, the coated positive electrode active particles satisfy at least one of the following characteristics (any numerical parameter in the following characteristics can also be selected from any appropriate numerical value or range in the context):

[0233] D coated positive electrode active particles v 50 is 0.1μm~20μm, and can be selected as 1μm~10μm; among them, D v 50 represents the particle size corresponding to when the cumulative volume distribution percentage of the multi-particle mixture reaches 50%;

[0234] The particle size of the positive electrode active body is 0.1 μm to 20 μm, and can be optionally 1 μm to 10 μm.

[0235] By adjusting the D v 50 and at least one of the particle size of the positive electrode active body can adjust the size of the coated positive electrode active particles. vControlling at least one of the parameters of the particle size of the active cathode particles (50 and the particle size of the active cathode particles) within the aforementioned ranges is beneficial for improving the discharge capacity of the coated active cathode particles and maintaining good contact between the coated active cathode particles and the sulfide-based electrolyte within the composite positive electrode. Smaller coated active cathode particles have shorter active ion transport channels within them, which is beneficial for improving the discharge capacity of the coated active cathode particles themselves. Larger coated active cathode particles are better encapsulated by the sulfide-based electrolyte, providing better interfacial contact with the sulfide-based electrolyte and improving battery cycling performance. Coated active cathode particles of relatively moderate size can enable batteries to achieve both high discharge capacity and excellent cycling performance.

[0236] Oxide cathode active materials, such as lithium transition metal oxides, and further examples such as high-nickel cathode active materials, high-voltage lithium cobalt oxide, or lithium-rich manganese cathode active materials, have high operating voltages and high specific capacities. However, due to the electrochemical potential difference between the oxide cathode active material and the sulfide electrolyte, these oxide cathode active materials spontaneously undergo elemental interdiffusion and chemical reactions when in direct contact with the sulfide electrolyte, forming a thick interfacial impedance layer. This increases interfacial resistance and affects solid-state battery performance. Furthermore, when the cathode active material in the cathode active particles includes an oxide cathode active material (such as a lithium transition metal oxide), the oxide cathode active material may release oxygen at high operating voltages (such as greater than 4.2V, such as during the first charge cycle into the high voltage region), which in turn attacks the sulfide solid electrolyte, leading to decomposition of the sulfide solid electrolyte. Oxidative decomposition of the sulfide solid electrolyte may increase interfacial impedance, negatively impacting discharge capacity and resulting in suboptimal electrochemical performance of the battery.

[0237] In some embodiments, the positive electrode active material in the coated positive electrode active particles includes an oxide positive electrode active material. In some embodiments, the oxide positive electrode active material may include but is not limited to lithium transition metal oxides.

[0238] In this application, unless otherwise specified, "oxide positive electrode active material" has the well-known meaning in the art, and refers to a positive electrode active material in the form of an oxide.

[0239] In this application, unless otherwise specified, "lithium transition metal oxide" has the commonly known meaning in the art, and refers to a positive electrode active material containing a transition metal element and lithium. Lithium transition metal oxide is an oxide positive electrode active material.

[0240] By arranging the aforementioned solid-state battery material in the positive electrode active material layer containing an oxide positive electrode active material (such as a lithium transition metal oxide), direct contact between the oxide positive electrode active material and the sulfide electrolyte can be hindered. By absorbing the oxygen that may be released by the positive electrode through the oxygen storage material, the attack of the released oxygen on the sulfide electrolyte can be suppressed, thereby reducing the oxidative decomposition of the sulfide electrolyte by oxygen, and suppressing the interfacial side reactions between the oxide positive electrode active material (such as a lithium transition metal oxide) and the sulfide electrolyte. The increase in interfacial impedance can be suppressed, which is beneficial to improving the stability of the sulfide electrolyte in the positive electrode layer during the cycle of the sulfide solid-state battery, thereby maintaining its excellent electrical conductivity, and is beneficial to long-term ionic conduction of the sulfide electrolyte and giving full play to the capacity of the positive electrode active particles, which can give the sulfide solid-state battery excellent high-voltage stability. Furthermore, the sulfide solid-state battery can have a higher first coulombic efficiency, a higher discharge capacity, a higher rate performance and better cycle performance. In addition, when a certain concentration of oxygen is stored in the oxygen storage material, the oxygen partial pressure on the surface of the positive electrode active particles increases, thereby further hindering the release of oxygen from the positive electrode active particles, thereby enhancing the structural stability of the positive electrode material.

[0241] In some embodiments, during the surface coating heat treatment process (such as 400°C to 600°C), the oxygen storage material can also capture part of the lattice oxygen in the positive electrode active material, form close contact with the positive electrode material, and form oxygen vacancies on the surface of the positive electrode active particles. The oxygen vacancies on the surface of the positive electrode active particles can promote the transmission of electrons and ions on the surface of the positive electrode active particles, thereby further improving the electrochemical performance of the solid-state battery.

[0242] When the positive electrode active material in the positive electrode active particles includes an oxide positive electrode active material (such as a lithium transition metal oxide), by adjusting at least one parameter of the weight ratio of the oxygen storage material in the coated particles and the thickness of the oxygen storage layer (for example, the weight ratio of the oxygen storage material in the coated particles (such as coated positive electrode active particles or coated electrolyte particles) can be controlled to be 0.1wt% to 10wt%, optionally 0.5wt% to 5wt%, and the thickness of the oxygen storage layer can also be controlled to be 0.1nm to 50nm, optionally 0.5nm to 10nm), it is possible to achieve both suppression of oxygen release and good interfacial ion transport. This can not only suppress oxygen release, improve the stability of the sulfide electrolyte, and achieve good discharge capacity and cycle performance, but also achieve good interfacial ion transport and fully utilize the discharge capacity of the positive electrode layer.

[0243] When the positive electrode active material in the positive electrode active particles includes an oxide positive electrode active material (such as lithium transition metal oxide), by adjusting the D v50 and at least one of the particle size of the positive electrode active body, the amount of the oxygen storage material in the oxygen storage layer relative to the positive electrode active material contained in the positive electrode active body can also be indirectly adjusted. v At least one parameter of the particle size of the positive electrode active body is controlled within the above range, which is beneficial for the oxygen storage material to provide sufficient oxygen absorption capacity, and is also beneficial for improving the discharge capacity of the coated positive electrode active particles and maintaining good contact between the coated positive electrode active particles and the sulfide-based electrolyte in the composite positive electrode.

[0244] Without limitation, the weight percentage of the oxide positive electrode active material (such as lithium transition metal oxide) in the positive electrode active body can be greater than or equal to 50wt% (i.e., ≥50wt%), further can be greater than or equal to 60wt%, further can be greater than or equal to 80wt%, further can be greater than or equal to 90wt%, further can be greater than or equal to 95wt%, and further can be 100wt%. The weight percentage of the oxide positive electrode active material (such as lithium transition metal oxide) in the positive electrode active body can also be any of the following weight percentages or an interval consisting of any two of the following weight percentages: 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 72wt%, 74wt%, 75wt%, 76wt%, 78wt%, 80wt%, 82wt%, 84wt%, 85wt%, 86wt%, 88wt%, 90wt%, 92wt%, 94wt%, 95wt%, 96wt%, 97wt%, 98wt%, 99wt%, 100wt%, etc.

[0245] In some embodiments, the oxide positive electrode active material (such as lithium transition metal oxide) includes one or more of a lithium cobalt oxide-type positive electrode active material, a high nickel positive electrode active material, a lithium manganese-rich positive electrode active material, and a modified form of any of the foregoing positive electrode active materials; the modified form may include one or more of a doping modification and a coating modification.

[0246] It can be understood that the lithium cobalt oxide type positive electrode active material contains Li element, Co element and O element.

[0247] In some embodiments, the atomic molar ratio of the Co element to the O element is x2:2, and satisfies 0.9≤x2≤1. x2 can also be any of the following values ​​or a range consisting of any two of the following values: 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 1.00, etc.

[0248] In some embodiments, the atomic molar ratio of Co to Li is x2, and satisfies 0.9≤x2≤1. x2 can also be any of the following values ​​or a range consisting of any two of the following values: 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 1.00, etc.

[0249] Without limitation, the lithium cobalt oxide positive electrode active material may contain Li, Co, and O in an atomic molar ratio of 1:x2:2, and satisfying 0.9≤x2≤1. Without limitation, x2 may also be any of the following values ​​or an interval consisting of any two of the following values: 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 1.00, etc.

[0250] In some embodiments, the lithium cobalt oxide positive electrode active material includes a chemical formula of LiCo x2 R 1-x2 In the lithium transition metal oxide of O2, R can be selected from one or more elements of Ni, Mg, Ti, Al, Cr, Fe, Nb and Ta.

[0251] It can be understood that the high nickel positive electrode active material contains Li element, Ni element and O element.

[0252] In some embodiments, the atomic molar ratio of Ni to O is y2:2, and satisfies 0.6≤y2≤1. Without limitation, y2 can also be any of the following values ​​or a range consisting of any two of the following values: 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.90, 0.95, 0.96, etc. Without limitation, y2 can also be selected from any of the following ranges: 0.8≤y2≤1, etc.

[0253] In some embodiments, the atomic molar ratio of Ni to Li is y2, and satisfies 0.6≤y2≤1. Without limitation, y2 can also be any of the following values ​​or a range consisting of any two of the following values: 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.90, 0.95, 0.96, etc. Without limitation, y2 can also be selected from any of the following ranges: 0.8≤y2≤1, etc.

[0254] Without limitation, the high nickel positive electrode active material may comprise Li, Ni, and O in an atomic molar ratio of 1:y2:2, and satisfying 0.6≤y2≤1. Without limitation, y2 may also be any of the following values ​​or an interval consisting of any two of the following values: 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.90, 0.95, 0.96, etc. Without limitation, y2 may also be selected from any of the following ranges: 0.8≤y2≤1, etc.

[0255] In some embodiments, the high-nickel positive electrode active material contains, in addition to nickel (Ni), cobalt (Co) and D, and the D element may be one or both of manganese (Mn) and aluminum (Al). In this case, the atomic number of nickel relative to lithium is y2. In some embodiments, y2 ≥ 0.6; further optionally, y2 ≥ 0.8; further optionally, y2 ≥ 0.9. y2 may also be any of the following values, or ≥ (greater than or equal to) any of the following values ​​and less than 1, or an interval selected from any two of the following values: 0.6, 0.7, 0.8, 0.9, 0.93, etc. y2 can also be selected from any of the following ranges: 0.6≤y2<1, 0.6≤y2≤1, 0.6≤y2≤0.95, 0.6≤y2≤0.94, 0.6≤y2≤0.93, 0.7≤y2<1, 0.7≤y2≤1, 0.7≤y2≤0.95, 0.7≤y2≤0.94, 0.7≤y2≤0.93, 0.8≤y2<1, 0.8≤y2≤1, 0.8≤y2≤0.95, 0.8≤y2≤0.94, 0.8≤y2≤0.93, 0.83≤y2<1, 0.83≤y2≤1, 0.83≤y2≤0.95, 0.83≤y2≤0.94, 0.83≤y2≤0.93, etc.

[0256] In some embodiments, the high nickel positive electrode active material comprises a chemical formula of LiNi y2 Co z2 D 1-y2-z2 Lithium transition metal oxide of O2, 0≤z2≤0.4, 0.6≤(y2+z2)≤1, D can be selected from one or more elements of Mn, Al, Zr, La, Ce, Ti, Mg, Nb, Ta, Mo and W. In some embodiments, D includes one or both of Mn element and Al element, and further, D can be selected from any one of Mn element and Al element. In some embodiments, D includes Mn element, and further, D can be selected from Mn element. Without limitation, z2 can also be any of the following values ​​or an interval consisting of any two of the following values: 0, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.36, 0.38, 0.39, 0.4, etc.

[0257] Non-restrictively, the lithium-rich manganese-based cathode active material contains Li element, Mn element and O element with an atomic molar ratio of (1 + p):(p + r(1 - p)):(2 + p), and satisfies 0 < p ≤ 1, 0 ≤ r ≤ 1. Non-restrictively, p can be any one of the following values, or selected from the intervals formed by any two of the following values, or greater than 0 and less than or equal to any one of the following values: 0.01, 0.02, 0.04, 0.05, 0.06, 0.08, 0.1, 0.12, 0.14, 0.15, 0.16, 0.18, 0.2, 0.22, 0.24, 0.25, 0.26, 0.28, 0.3, 0.32, 0.35, 0.36, 0.38, 0.4, 0.42, 0.44, 0.45, 0.46, 0.48, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.92, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, 1, etc. Non-restrictively, r can be any one of the following values or selected from the intervals formed by any two of the following values: 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, etc. p can also be selected from any one of the following ranges: 0.2 ≤ p ≤ 1.

[0258] In some embodiments, the lithium-rich manganese-based cathode active material includes a lithium transition metal oxide with the chemical formula pLi2MnO3·(1 - p)LiZO2, and Z can be selected from, but not limited to, one or more elements among nickel (Ni), cobalt (Co), manganese (Mn), chromium (Cr), iron (Fe), aluminum (Al), niobium (Nb), molybdenum (Mo) and ruthenium (Ru).

[0259] Lithium transition metal oxides such as lithium cobalt oxide-based cathode active material, high-nickel cathode active material, lithium-rich manganese-based cathode active material, etc. are prone to releasing oxygen at high working voltages. When using these lithium transition metal oxides as the cathode active material in the cathode active particles, by arranging the aforementioned solid-state battery material in the cathode active material layer, it is beneficial to achieve both high energy density and long cycle performance of the sulfide solid-state battery under the possible oxygen release at the cathode.

[0260] When the solid-state battery material arranged in the cathode active material layer includes the aforementioned coated cathode active particles, further, it is also beneficial to inhibit the oxygen release of the cathode material, improve the crystal structure stability of the cathode active particles during battery cycling, inhibit the formation of the surface rock salt phase, and is beneficial to fully exert the cathode capacity and improve the long cycle performance of the battery.

[0261] In some embodiments, D of the coated electrolyte particles v50 is 1 nm to 20 μm, and can be 50 nm to 5 μm, or any of the following sizes or an interval consisting of any two of the following sizes: 1 nm, 5 nm, 10 nm, 20 nm, 50 nm, 60 nm, 80 nm, 100 nm (0.1 μm), 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.8 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3μm, 3.5μm, 4μm, 4.5μm, 5μm, 5.5μm, 6μm, 6.5μm, 7μm, 7.5μm, 8μm, 8.5μm, 9μm, 9.5μm, 10μm, 10.5μm, 11μm, 11.5μm, 12μm , 12.5μm, 13μm, 13.5μm, 14μm, 14.5μm, 15μm, 15.5μm, 16μm, 16.5μm, 17μm, 17.5μm, 18μm, 18.5μm, 19μm, 19.5μm, 20μm, etc.

[0262] In some embodiments, the particle size of the solid electrolyte body is 1 nm to 20 μm, optionally 50 nm to 5 μm, or any of the following sizes or an interval consisting of any two of the following sizes: , It can also be any of the following sizes or an interval consisting of any two of the following sizes: 1 nm, 5 nm, 10 nm, 20 nm, 50 mn, 60 nm, 80 nm, 100 nm (0.1 μm), 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.8 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm , 3μm, 3.5μm, 4μm, 4.5μm, 5μm, 5.5μm, 6μm, 6.5μm, 7μm, 7.5μm, 8μm, 8.5μm, 9μm, 9.5μm, 10μm, 10.5μm, 11μm, 11.5μm, 12μm m, 12.5μm, 13μm, 13.5μm, 14μm, 14.5μm, 15μm, 15.5μm, 16μm, 16.5μm, 17μm, 17.5μm, 18μm, 18.5μm, 19μm, 19.5μm, 20μm, etc.

[0263] In some embodiments, the coated electrolyte particles satisfy at least one of the following characteristics (any numerical parameter in the following characteristics can also be selected from any appropriate numerical value or range in the context):

[0264] D coated electrolyte particles v 50 is 1nm~20μm, and can be selected as 50nm~5μm; among them, D v 50 represents the particle size corresponding to when the cumulative volume distribution percentage of the multi-particle mixture reaches 50%;

[0265] The particle size of the solid electrolyte body is 1 nm to 20 μm, and can be optionally 50 nm to 5 μm.

[0266] By adjusting the D v 50 and the particle size of the solid electrolyte body can adjust the size of the coated electrolyte particles. v Regulating at least one of the particle size of the solid electrolyte particles (50) and the particle size of the solid electrolyte body within the aforementioned range is beneficial for improving the overall ion conductivity of the film layer in which the coated electrolyte particles are located, providing a better electrical contact network, and taking into account manufacturing costs. This can adjust the manufacturing cost of the solid electrolyte body and the amount of oxygen storage material required to prepare the coated electrolyte particles. A relatively small particle size of the coated electrolyte particles is beneficial for improving the electrical contact between the positive electrode active particles within the positive electrode film or positive electrode layer, thereby promoting the full capacity of the solid-state battery. A relatively moderate particle size of the coated electrolyte particles is easier to manufacture.

[0267] In some embodiments, the sulfide electrolyte in the coated electrolyte particles may include one or more of an argyrodite-type sulfide electrolyte, an LGPS-type sulfide electrolyte, and a lithium sulfide pentasulfide diphosphorus complex-type sulfide electrolyte.

[0268] Unless otherwise specified, the argyrodite-type sulfide electrolyte has an argyrodite-type crystal structure. 6±s P 1-j A j S 5±s-t B t X 1±s A sulfide electrolyte, wherein 0≤j<1, 0≤t<1, 0≤s<1, A may be selected from but not limited to one or more elements of Ge, Si, Sn and Sb, B may be one or more elements of O, Se and Te, and X may be selected from one or more elements of Cl, Br, I and F.

[0269] Unless otherwise specified, the LGPS sulfide electrolyte has an LGPS type crystal phase structure. Without limitation, the LGPS sulfide electrolyte may include a chemical formula of Li 10±δ5 Ge 1-g G g P 2-q Q q S 12-w W w A sulfide electrolyte, wherein 0≤δ5<1, 0≤g≤1, 0≤q≤2, 0≤w<1, G is selected from one or two elements of Si and Sn, Q is Sb, and W is selected from one or more elements of O, Se, Te, Cl, Br, I and F.

[0270] Non - restrictively, the sulfide electrolyte of the lithium sulfide - phosphorus pentasulfide composite type may include a sulfide electrolyte with the chemical formula (100 - u - v)Li2S·uP2S5·vM m N n where 0 < u < 100, 0 ≤ v < 100, 0 ≤ u + v < 100, 0 ≤ m < 4, 0 ≤ n < 6, M may be selected from one or more elements including but not limited to Li, B, Ge, Si, Sn, and Sb, and N may be selected from one or more elements including S, Se, Te, O, Cl, Br, I, and F.

[0271] By using the aforementioned solid - state battery materials, sulfide electrolytes with high ion - transport rates can be more flexibly used in sulfide solid - state batteries, greatly reducing the material - selection limitations of sulfide electrolytes.

[0272] In some embodiments, the sulfide electrolyte in the coated electrolyte particles may include at least one of a binary sulfide solid system and a ternary sulfide solid system. Non - restrictively, the binary sulfide solid system may include one or more of Li2S - P2S5, Li2S - SiS2, Li2S - GeS2, and Li2S - B2S3. Non - restrictively, the ternary sulfide solid system may include one or more of thio - argentite - type sulfide electrolytes, Li2S - MeS2 - P2S5 ternary sulfide electrolytes, lithium - germanium - phosphorus - sulfur - type sulfide electrolytes, Li2S - P2S5 - MS ternary sulfide electrolytes, Li2S - P2S5 - MCl ternary sulfide electrolytes, and thio - LISICON - type sulfide electrolytes; where Me may include one or more elements including silicon (Si), germanium (Ge), tin (Sn), and aluminum (Al), and may further be selected from one or more of Si, Ge, Sn, and Al; M may include one or more elements including Ge, Al, Sn, lead (Pb), antimony (Sb), Si, and arsenic (As), and may further be selected from one or more of Ge, Al, Sn, Pb, Sb, Si, and As.

[0273] In some embodiments, the solid - state battery material is a sulfide solid - state battery material. The definition of "sulfide solid - state battery material" can be referred to above.

[0274] In some embodiments, the solid - state battery material is a sulfide all - solid - state battery material. The definition of "sulfide all - solid - state battery material" can be referred to above. [[ID=I9]]

[0275] In the second aspect of the present application, a positive active material layer is provided, which includes the solid - state battery material described in the first aspect of the present application.

[0276] As a non-limiting example, the positive electrode active material layer may be present in a separate positive electrode membrane or in a positive electrode layer of a solid-state battery.

[0277] It can be understood that the positive electrode active material layer provided in the second aspect of the present application includes at least one of coated positive electrode active particles and coated electrolyte particles. When the positive electrode active material layer is applied to a sulfide solid-state battery, the oxygen storage material in the oxygen storage layer absorbs oxygen, which can reduce the contact probability between the sulfide electrolyte and oxygen, thereby improving the chemical stability of the sulfide electrolyte during the battery preparation process, and is conducive to giving full play to the role of the sulfide electrolyte in rapid ion conduction, thereby promoting the stable operation of the solid-state battery and improving the discharge capacity and cycle performance of the sulfide solid-state battery. In addition, the oxygen storage layer provided on the surface of the coated electrolyte particles can also reduce or isolate the direct contact between the sulfide electrolyte and moisture in the air, inhibit the decomposition of the sulfide electrolyte and the generation of hydrogen sulfide gas, and is conducive to improving the chemical stability of the sulfide electrolyte.

[0278] As defined above, the positive electrode active material layer includes at least positive electrode active particles, which include positive electrode active materials. In some embodiments, the positive electrode active materials in the positive electrode active particles include oxide positive electrode active materials, and further, the positive electrode active materials include lithium transition metal oxides.

[0279] Non-limitingly, the oxide positive electrode active material in the positive electrode active material (such as lithium transition metal oxide) may include lithium transition metal oxides that are well known in the art and can be used as positive electrode active materials in solid-state batteries, but are not limited thereto. Examples of lithium transition metal oxides may include, but are not limited to, 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 modified compounds thereof. Non-limiting examples of lithium cobalt oxide may include LiCoO2; non-limiting examples of lithium nickel oxide may include LiNiO2; non-limiting examples of lithium manganese oxide may include LiMnO2, LiMn2O4, etc.; non-limiting examples of lithium nickel cobalt manganese oxide may include LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2 (also referred to as NCM 333 ), LiNi 0.5 Co 0.2 Mn 0.3 O2 (also referred to as NCM 523 ), LiNi 0.5 Co 0.25 Mn 0.25 O2 (also referred to as NCM 211 ), LiNi 0.6Co 0.2 Mn 0.2 O2 (also referred to as NCM 622 ), LiNi 0.8 Co 0.1 Mn 0.1 O2 (also referred to as NCM 811 ) etc. Non-limiting examples of lithium nickel cobalt aluminum oxide may include LiNi 0.80 Co 0.15 Al 0.05 O2.

[0280] Taking a solid-state battery in which active ions include lithium ions as an example, it is understandable that the solid-state battery will be accompanied by the deintercalation and consumption of lithium (Li) during the charge and discharge process, and the content of Li in the positive electrode layer (including the positive electrode film in the context) is different when the battery is discharged to different states. In the exemplary description of the positive electrode active material in this application, unless otherwise specified, the content of Li can be the initial state of the material or the non-initial state after the charge and discharge cycle. The positive electrode active material is applied to the positive electrode layer in the solid-state battery system. After the charge and discharge cycle, the content of Li in the positive electrode active material contained in the positive electrode layer usually changes. Among them, the content of Li can be measured using atomic molar content, but is not limited to this. Regarding "the content of Li is the initial state of the material", the initial state of the material refers to the state before being placed in the positive electrode layer. It can be understood that new materials or new substances obtained by appropriate modification on the basis of the listed positive electrode active materials are also within the scope of positive electrode active materials. The aforementioned appropriate modification refers to an acceptable modification method for the positive electrode active material, and a non-limiting example is coating modification. In the exemplary descriptions of the positive electrode active material in this application, the oxygen (O) content is generally a theoretical value. Lattice oxygen release will cause the atomic molar content of oxygen to change, and the actual O content will fluctuate. The O content can be measured by atomic molar content, but is not limited to this.

[0281] In some embodiments, in addition to oxide positive electrode active materials (such as lithium transition metal oxides), the positive electrode active material may also include other positive electrode active materials that are well known in the art and can be used for solid-state batteries. As a non-limiting example, other positive electrode active materials that can be used for solid-state batteries may include one or more of the following materials: lithium-containing phosphates with an olivine structure and modified compounds thereof. However, the present application is not limited to these materials, and other existing materials that can be used as positive electrode active materials for solid-state batteries may also be used. These positive electrode active materials can be used alone or in combination of two or more. Non-limiting examples of lithium-containing phosphates with an olivine structure may include, but are not limited to, one or more of lithium iron phosphate, a composite material of lithium iron phosphate and carbon, lithium manganese phosphate, a composite material of lithium manganese phosphate and carbon, lithium manganese iron phosphate, and a composite material of lithium manganese iron phosphate and carbon. An example of lithium iron phosphate is LiFePO4 (also referred to as LFP). An example of lithium manganese phosphate is LiMnPO4.

[0282] In some embodiments, the lithium transition metal oxide includes 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, lithium manganese-rich positive electrode active material (definition can be found below) and one or more modified forms of any of the foregoing positive electrode active materials; the modified form can include one or more of doping modification and coating modification.

[0283] It is understood that the positive electrode active material layer includes positive electrode active particles. Without limitation, the weight proportion of the positive electrode active particles in the positive electrode active material layer is 70 wt% to 99 wt%, and optionally 80 wt% to 95 wt%. Without limitation, the weight proportion of the positive electrode electrolyte particles in the positive electrode active material layer can be 0.1 wt% to 30 wt%, and optionally 5 wt% to 20 wt%.

[0284] In some embodiments, the positive electrode active particles include coated positive electrode active particles. Without limitation, the weight proportion of the coated positive electrode active particles in the positive electrode active material layer can be 70wt% to 99wt%, optionally 80wt% to 95wt%. The weight proportion of the coated positive electrode active particles in the positive electrode active material layer can also be any of the following weight percentages or an interval consisting of any two of the following weight percentages: 70wt%, 72wt%, 74wt%, 75wt%, 76wt%, 78wt%, 80wt%, 82wt%, 84wt%, 85wt%, 86wt%, 88wt%, 90wt%, 92wt%, 94wt%, 95wt%, 96wt%, 97wt%, 98wt%, 99wt%, etc.

[0285] In some embodiments, the positive electrode electrolyte particles include a sulfide-based electrolyte.

[0286] The sulfide electrolyte contained in the sulfide-based electrolyte has very good ion conductivity. By setting the sulfide-based electrolyte in the positive electrode layer, the charge transfer efficiency between the positive electrode active material and the outside world and the full release of its capacity can be better promoted.

[0287] In some embodiments, the positive active material layer includes positive electrolyte particles.

[0288] In some embodiments, the positive electrode electrolyte particles include coated electrolyte particles. In this case, the positive electrode active material layer includes a sulfide-based electrolyte. Without limitation, the weight percentage of the coated electrolyte particles in the positive electrode active material layer may be 0.1 wt% to 30 wt%, and optionally 5 wt% to 20 wt%. The weight proportion of the coated electrolyte particles in the positive electrode active material layer can also be any of the following weight percentages or an interval consisting of any two of the following weight percentages: 0.1wt%, 0.2wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.8wt%, 1wt%, 1.2wt%, 1.5wt%, 1.6wt%, 1.8wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 12wt%, 14wt%, 15wt%, 16wt%, 18wt%, 20wt%, 22wt%, 24wt%, 25wt%, 26wt%, 28wt%, 30wt%, etc.

[0289] In some embodiments, the positive electrode active material layer includes positive electrode active particles and positive electrode electrolyte particles.

[0290] In some embodiments, the positive electrode active material layer satisfies at least one of the following characteristics (any numerical parameter in the following characteristics can also be selected from any appropriate numerical value or range in the context):

[0291] In some embodiments, the positive electrode active particles include coated positive electrode active particles, and the weight proportion of the coated positive electrode active particles in the positive electrode active material layer is 70 wt % to 99 wt %, optionally 80 wt % to 95 wt %;

[0292] The positive electrode electrolyte particles include coated electrolyte particles, and the weight proportion of the coated electrolyte particles in the positive electrode active material layer is 0.1 wt% to 30 wt%, and can be optionally 5 wt% to 20 wt%.

[0293] By controlling the weight ratio of the coated positive electrode active particles in the positive electrode active material layer within the above range, it is beneficial to achieve both high energy density and cycle stability.

[0294] When the positive electrode membrane also includes a sulfide-based electrolyte, by controlling the weight proportion of the coated positive electrode active particles in the positive electrode active material layer within the above range, it is also beneficial to achieve a balance between high energy density and reducing the oxidative decomposition of the sulfide electrolyte contained in the sulfide-based electrolyte.

[0295] The weight percentage of the coated electrolyte particles in the positive electrode active material layer can be controlled within the aforementioned range, which is beneficial for the positive electrode film to provide better overall ion conductivity.

[0296] In some embodiments, the positive electrode active material layer includes at least positive electrode active particles and positive electrode electrolyte particles. The positive electrode active particles include a positive electrode active material, and the positive electrode electrolyte particles include a sulfide-based electrolyte. The positive electrode active material in the positive electrode active material layer and the sulfide-based electrolyte are separated by an oxygen storage layer. The oxygen storage layer can be located on the surface of at least one of the positive electrode active particles and the positive electrode electrolyte particles, can be located only on the surface of the positive electrode active particles (in which case, corresponding to coating the positive electrode active particles), can be located only on the surface of the positive electrode electrolyte particles (in which case, corresponding to coating the electrolyte surface), or can be located on the surfaces of both the positive electrode active particles and the positive electrode electrolyte particles. See Figures 4 to 8 for details.

[0297] In some embodiments, the positive electrode active material layer 220 includes coated electrolyte particles 810 , which may be referred to as a positive electrode active material layer 220 a , as shown in FIG. 4 .

[0298] In some embodiments, the positive electrode active material layer 220 includes coated positive electrode active particles 820 , which may be referred to as the positive electrode active material layer 220 b , as shown in FIG5 .

[0299] In some embodiments, the positive electrode active material layer 220 includes coated electrolyte particles 810 and coated positive electrode active particles 820, which may be referred to as a positive electrode active material layer 220c.

[0300] In some embodiments, the positive electrode active material layer 220 includes coated positive electrode active particles 820 and a sulfide-based electrolyte 910 without an oxygen storage layer, and may be referred to as a positive electrode active material layer 220d , as shown in FIG. 7 .

[0301] In some embodiments, the positive electrode active material layer 220 includes coated electrolyte particles 810 and positive electrode active particles 920 without an oxygen storage layer, which can be referred to as a positive electrode active material layer 220e , as shown in FIG8 .

[0302] In some embodiments, the positive electrode active material layer includes a conductive agent (which may be referred to as a positive electrode conductive agent). As a non-limiting example, the positive electrode conductive agent may be a carbon conductive agent. Non-limitingly, the carbon conductive agent may include one or more of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers. In some embodiments, the positive electrode conductive agent may include but is not limited to one or more of SP, KS-6, acetylene black, Ketjen black ECP with a branched structure, SFG-6, vapor-grown carbon fiber VGCF, carbon nanotubes (CNTs) and graphene. Non-limitingly, the weight percentage of the positive electrode conductive agent in the positive electrode active material layer may be 0 to 10 wt%, further 0 to 8 wt%, further 0 to 5 wt%, further 0.1 wt% to 3 wt%, based on the total weight of the positive electrode active material layer. The weight percentage of the positive electrode conductive agent in the positive electrode active material layer can also be 0.1wt% to 5wt%, 0.2wt% to 5wt%, 0.5wt% to 5wt%, 0.1wt% to 3wt%, etc. When the positive electrode material is prepared into the positive electrode active material layer by a dry method, the positive electrode conductive agent can be provided in the positive electrode material to improve the electron conductivity of the positive electrode active material layer.

[0303] In some embodiments, the positive electrode active material layer optionally includes a binder. As a non-limiting example, the binder may include one or more of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer and fluorine-containing acrylate resin. Typically, the weight percentage of the binder in the positive electrode active material layer may be 0 to 10 wt%, further 0 to 8 wt%, further 0.1 wt% to 5 wt%, further 1 wt% to 5 wt%, based on the total weight of the positive electrode active material layer. When the positive electrode material is formulated into a positive electrode slurry by a wet method and then prepared into a positive electrode active material layer, a binder may be provided in the positive electrode slurry to assist in film formation and to promote the formation of a good electrical contact network between the active particles of the positive electrode active material layer.

[0304] Without limitation, the positive electrode active material layer may include positive electrode active particles, positive electrode electrolyte particles, a positive electrode conductive agent, and a binder. The type and content of each component can be found in the context of this application.

[0305] In this application, unless otherwise specified, a positive electrode active material layer sample can be obtained from a solid-state battery in the following manner: the battery can be disassembled to obtain an active material layer sample of the electrode plate, and the active material layer can be further analyzed by the following method: the nano-spatial dynamic resolution and layer-by-layer cutting technology of FIB-SEM are used to reconstruct the three-dimensional structure of the sample, and the distribution and proportion of each element are obtained by combining EDS element energy spectrum analysis, and finally the composition and thickness and other parameters of each structural layer of the active material layer are obtained through software quantitative analysis.

[0306] In this application, unless otherwise specified, the types and contents of components such as the positive electrode active particles (including coated positive electrode active particles) and the positive electrode electrolyte particles (including coated electrolyte particles) in the positive electrode active material layer of the solid-state battery can be detected by the following method: the structure and composition analysis of the positive electrode active material layer can be tested and analyzed by focused electron beam (FIB) technology, scanning electron microscopy (SEM) and elemental analysis technology, for example, it can be obtained by combining cryo-focused electron beam (FIB) continuous sectioning, cross-section SEM morphology observation, energy dispersive spectroscopy (EDS) element spectrum and three-dimensional reconstruction analysis software analysis. For example, a cryo-focused ion beam (FIB) is used to finely slice the sample layer by layer in the transverse direction at different thickness positions (the minimum scale can reach nanometer-level thin slices), and separate different layers of samples at different thickness positions. It can also be tested by scanning electron microscopy (SEM), and the morphology, structure and element distribution of each layer of the cross section are analyzed under FIB continuous sectioning. The three-dimensional structure of the sample can be reconstructed in combination with three-dimensional structure reconstruction software, and the mass and / or volume of different areas of the sample to be tested can be estimated. As a non-limiting example, the above parameters may be tested and analyzed using a FEI Scios 2HiVac device.

[0307] In the present application, unless otherwise specified, the particle size and particle size distribution of each solid particle in the positive electrode active material layer sample of the solid-state battery can be analyzed in the following manner, which may include analyzing the particle size and particle size distribution of particle components such as positive electrode active particles and positive electrode electrolyte particles: In the present application, unless otherwise specified, FIB-SEM combined with EDS testing can be used to obtain a two-dimensional image with different color markings for different components, and particle components such as positive electrode active particles and positive electrode electrolyte particles can be distinguished according to the type of components. The particle size and particle size distribution of particle components such as positive electrode active particles and positive electrode electrolyte particles can be analyzed using the software provided by the EDS instrument.

[0308] In the third aspect of the present application, a positive electrode membrane is provided, which includes a positive electrode active material layer, the positive electrode active material layer includes the solid-state battery material described in the first aspect of the present application, or the positive electrode active material layer is the positive electrode active material layer described in the second aspect of the present application.

[0309] Without limitation, the positive electrode film can be a standalone positive electrode film sheet used in assembling a solid-state battery. Alternatively, the positive electrode film can be a positive electrode film layer present in a multilayer composite structure. For example, the constituent materials of the positive electrode film layer can be pressed into a film on the surface of a solid electrolyte layer. As a non-limiting example, the positive electrode film can be a positive electrode layer or a portion of a positive electrode layer of a solid-state battery.

[0310] In this application, unless otherwise specified, "positive electrode film" refers to a film that can be used as a positive electrode for a solid-state battery, including at least a positive electrode active material layer and usually also a positive electrode current collector. The positive electrode film includes the positive electrode active material layer described in the second aspect of this application.

[0311] In some embodiments, the positive electrode film includes a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector. The definition of the positive electrode active material layer can be found in the above text.

[0312] In some embodiments, referring to FIG. 13 , the positive electrode film 20 includes a positive electrode current collector 210 and a positive electrode active material layer 220 located on one side of the positive electrode current collector 210 .

[0313] In some embodiments, referring to FIG. 14 , the positive electrode film 20 includes a positive electrode current collector 210 and positive electrode active material layers 220 located on both sides of the positive electrode current collector 210 .

[0314] Without limitation, in the positive electrode film or positive electrode layer, the thickness of the positive electrode active material layer is 30μm to 400μm, optionally 60μm to 130μm, and can also be any of the following thicknesses or an interval consisting of any two of the following thicknesses: 30μm, 40μm, 50μm, 60μm, 80μm, 100μm, 120μm, 130μm, 140μm, 150μm, 160μm, 180μm, 200μm, etc. The thickness of the positive electrode active material layer may also be any of the following ranges: 40 μm to 400 μm, 40 μm to 300 μm, 40 μm to 200 μm, 40 μm to 150 μm, 40 μm to 130 μm, 40 μm to 120 μm, 50 μm to 400 μm, 50 μm to 300 μm, 50 μm to 200 μm, 50 μm to 150 μm, 50 μm to 130 μm, 50 μm to 120 μm, μm~120μm, 60μm~400μm, 60μm~300μm, 60μm~200μm, 60μm~150μm, 60μm~120μm, 80μm~400 μm, 80μm~300μm, 80μm~200μm, 80μm~150μm, 80μm~120μm, 100μm~200μm, 120μm~260μm, etc.

[0315] In this application, unless otherwise specified, the "thickness of the positive electrode active material layer" in the positive electrode film refers to the total thickness of the positive electrode film. When the positive electrode active material layer is provided on both sides of the positive electrode current collector, the thickness of the positive electrode active material layer refers to the sum of the thicknesses of both sides.

[0316] As a non-limiting example, the positive electrode current collector has two surfaces facing away from each other in its thickness direction, and the positive electrode active material layer is disposed on either or both of the two facing surfaces of the positive electrode current collector.

[0317] In some embodiments, the positive electrode current collector may be a metal foil or a composite current collector. For example, aluminum foil may be used as the metal foil. In the positive electrode current collector, the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer. In the positive electrode current collector, the composite current collector may be obtained by forming a metal material on a polymer material substrate. In the positive electrode current collector, non-limiting examples of the metal material may include at least one of aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy. In the positive electrode current collector, non-limiting examples of the polymer material substrate may include one or more of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.

[0318] The positive electrode film can be prepared by a dry process or a wet process. For example, a dry process can be used to press the positive electrode film. Alternatively, a wet process can be used to apply the positive electrode film and then dry the positive electrode film.

[0319] In some embodiments, the positive electrode membrane (the positive electrode membrane can be used as the positive electrode sheet) can be prepared in the following manner: the components for preparing the positive electrode membrane, such as positive electrode active particles, positive electrode electrolyte particles, positive electrode conductive agent, binder and any other components are dry-mixed, and then the mixed material is heated and pressurized to form a mass material, which is hot rolled to form a self-supporting positive electrode sheet, and the self-supporting positive electrode sheet is hot-rolled with the positive electrode collector. The self-supporting positive electrode sheet can be compounded on at least one side (one side or two sides) of the positive electrode collector to obtain a positive electrode membrane. Without limitation, a double planetary mixer can be used for dry mixing. Without limitation, an internal mixer can be used for heating, pressurizing and kneading. Without limitation, the temperature for hot rolling can be 75°C to 85°C, and further such as 78°C, 80°C, 82°C, etc. The method of assembling solid-state batteries using positive electrode membranes can be suitable for industrial mass production.

[0320] In some embodiments, a positive electrode membrane can be prepared by dispersing the components used to prepare the positive electrode membrane, such as the positive electrode active particles, positive electrode electrolyte particles, positive electrode conductive agent, binder, and any other components, in an organic solvent to form a positive electrode slurry. Furthermore, the positive electrode slurry is coated on at least one surface of a positive electrode current collector. After drying and cold pressing, the positive electrode membrane can be obtained. The cold pressing can be performed using a cold rolling mill. The organic solvent in the positive electrode slurry can include one or more of p-xylene, trimethylbenzene, butyl butyrate, heptane, and can further be p-xylene. The surface of the positive electrode current collector coated with the positive electrode slurry can be a single surface of the positive electrode current collector or both surfaces of the positive electrode current collector. The solid content of the positive electrode slurry can be 40 wt% to 80 wt%. The viscosity of the positive electrode slurry at room temperature can be adjusted to 5000 mPa·s to 25000 mPa·s. When applying the positive electrode slurry, the coating unit area density based on dry weight (excluding solvent) can be 15 mg / cm 2 ~35mg / cm 2 The compaction density of the positive electrode membrane can be 3.0g / cm 3 ~3.6g / cm 3 , optional 3.3g / cm 3 ~3.5g / cm 3 .

[0321] The “compacted density” used in this application has a meaning well known in the art and is one of the reference indicators of material energy density. In this application, unless otherwise specified, the compacted density of an electrode layer refers to the ratio of the mass of the electrode active material layer to its volume. The compacted density of a positive electrode layer, a positive electrode sheet, a positive electrode film or a positive electrode membrane refers to the ratio of the mass of the positive electrode active material layer to its volume, and the compacted density of a negative electrode layer, a negative electrode sheet, a negative electrode film or a negative electrode membrane refers to the ratio of the mass of the negative electrode active material layer to its volume.

[0322] In another aspect of the present application, a positive electrode membrane is provided, which includes a positive electrode current collector and a positive electrode active material layer located on at least one side of the positive electrode current collector. The positive electrode active material layer is the positive electrode active material layer described in the second aspect of the present application.

[0323] The positive electrode film can be directly used as a positive electrode sheet to assemble a solid-state battery, but is not limited to this.

[0324] In a fourth aspect of the present application, a solid electrolyte membrane is provided, which includes the solid-state battery material described in the first aspect of the present application, and the coated particles are coated electrolyte particles.

[0325] Without limitation, the solid electrolyte membrane may be an independent solid electrolyte membrane sheet, which is then used to assemble a solid-state battery; the solid electrolyte membrane may also be a solid electrolyte membrane layer present in a composite structure.

[0326] This solid electrolyte membrane includes coated electrolyte particles. The oxygen storage layer arranged on the surface of the coated electrolyte particles can reduce or isolate the decomposition effect of oxygen in the air on the sulfide electrolyte, and can also reduce or isolate the direct contact between the sulfide electrolyte and moisture in the air, and can inhibit the decomposition of the sulfide electrolyte and the generation of hydrogen sulfide gas, thereby improving the chemical stability of the sulfide electrolyte in the battery preparation process and the stability of the ion conductivity of the solid electrolyte membrane, promoting the stable operation of the solid-state battery, and being beneficial to improving the discharge capacity and cycle performance of the sulfide solid-state battery.

[0327] In some embodiments, the solid electrolyte membrane 10 is a solid electrolyte membrane 10 a including coated electrolyte particles 810 , as shown in FIG. 9 .

[0328] The solid electrolyte membrane can be prepared using conventional methods in the field of solid-state batteries, such as pressing a solid electrolyte material into a membrane. In some embodiments of the present application, a solid electrolyte material including coated electrolyte particles can be pressed into a membrane, and further, the coated electrolyte particles can be pressed into a membrane. In other words, the solid electrolyte membrane can include coated electrolyte particles or can be composed of coated electrolyte particles.

[0329] In a fifth aspect of the present application, a solid-state battery is provided, which includes the solid-state battery material described in the first aspect of the present application.

[0330] In some embodiments, a solid-state battery is provided, comprising a cathode layer, a solid electrolyte layer, and an anode layer;

[0331] Among them, solid-state batteries can meet one or more of the following characteristics:

[0332] The positive electrode layer includes the positive electrode active material layer described in the second aspect of the present application;

[0333] The positive electrode layer includes the positive electrode film described in the third aspect of the present application;

[0334] The solid electrolyte layer includes the solid electrolyte membrane described in the fourth aspect of the present application.

[0335] In some embodiments, a solid-state battery is provided, comprising a positive electrode layer, a solid electrolyte layer, and a negative electrode layer;

[0336] The solid-state battery comprises one or more solid-state battery materials described in the first aspect of the present application;

[0337] When the coated particles include coated positive electrode active particles, the coated positive electrode active particles are located in the positive electrode layer;

[0338] When the coated particles include coated electrolyte particles, the coated electrolyte particles are located in at least one of the positive electrode layer and the solid electrolyte layer.

[0339] In some embodiments, a solid-state battery is provided, comprising a positive electrode layer, a solid electrolyte layer, and a negative electrode layer; the positive electrode layer comprises a positive electrode active material layer, the positive electrode active material layer comprises positive electrode active particles and positive electrode electrolyte particles;

[0340] At least one of the solid electrolyte layer and the positive electrode electrolyte particles comprises a sulfide electrolyte;

[0341] The solid-state battery comprises one or more solid-state battery materials described in the first aspect of the present application;

[0342] Solid-state batteries can meet at least one of the following characteristics:

[0343] (ta1) at least a portion of the positive electrode electrolyte particles contain a sulfide electrolyte (i.e., at least a portion of the positive electrode electrolyte particles are sulfide-based electrolytes), and the positive electrode active material layer includes at least one of coated positive electrode active particles and coated electrolyte particles; and

[0344] (ta2) The solid electrolyte layer includes coated electrolyte particles.

[0345] In some embodiments, the positive electrode electrolyte particles are sulfide-based electrolytes, and the positive electrode active material layer includes at least one of coated positive electrode active particles and coated electrolyte particles.

[0346] In some embodiments, a solid-state battery may meet one or more of the following characteristics:

[0347] The solid electrolyte layer and the positive electrode electrolyte particles both contain a sulfide electrolyte. The sulfide electrolyte contained in the positive electrode electrolyte particles is referred to as a first sulfide electrolyte, and the sulfide electrolyte contained in the solid electrolyte layer is referred to as a second sulfide electrolyte. The first sulfide electrolyte and the second sulfide electrolyte may be the same or different.

[0348] The positive electrode electrolyte particles contain a sulfide electrolyte, and at least one of the positive electrode active particles and the positive electrode electrolyte particles includes the aforementioned coated particles.

[0349] In some embodiments, the positive electrode electrolyte particles include a sulfide electrolyte, and at least one of the positive electrode active particles and the positive electrode electrolyte particles is the aforementioned coated particle.

[0350] In some embodiments, the positive electrode electrolyte particles include a sulfide electrolyte, and the positive electrode active particles include coated positive electrode active particles, and may further be coated positive electrode active particles.

[0351] In some embodiments, the positive electrode electrolyte particles include a sulfide electrolyte, and the positive electrode electrolyte particles include coated electrolyte particles, and may further be coated electrolyte particles.

[0352] In some embodiments, the positive electrode electrolyte particles comprise a sulfide electrolyte, the positive electrode active particles comprise coated positive electrode active particles, and the positive electrode electrolyte particles comprise coated electrolyte particles; alternatively, the positive electrode active particles are coated positive electrode active particles, and the positive electrode electrolyte particles are coated electrolyte particles.

[0353] As mentioned above, for a solid-state battery (sulfide solid-state battery) in which the aforementioned solid-state battery material is arranged at at least one of the positive electrode layer and the solid electrolyte layer, when at least one of coated positive electrode active particles and coated electrolyte particles is used in the positive electrode layer, or when coated electrolyte particles are used in the solid electrolyte layer, or when the aforementioned solid-state battery material is used in both the positive electrode layer and the solid electrolyte layer, it is beneficial to improve the discharge capacity and cycle performance of the solid-state battery.

[0354] In some embodiments, the solid electrolyte membrane 10 used to prepare a solid-state battery is a solid electrolyte membrane 10 b including a sulfide-based electrolyte 910 without an oxygen storage layer, as shown in FIG. 10 .

[0355] In some embodiments, the solid electrolyte layer 100 is a solid electrolyte layer 100 a including coated electrolyte particles 810 , as shown in FIG. 11 .

[0356] In some embodiments, the solid electrolyte layer 100 is a solid electrolyte layer 100 b including a sulfide-based electrolyte 910 without an oxygen storage layer, as shown in FIG. 12 .

[0357] In a sixth aspect of the present application, an electrical device is provided, which includes the solid-state battery described in the fourth aspect of the present application.

[0358] In the seventh aspect of the present application, the application of the solid-state battery material described in the first aspect of the present application, or the positive electrode active material layer described in the second aspect of the present application, or the positive electrode film described in the third aspect of the present application, or the solid electrolyte membrane described in the fourth aspect of the present application in the preparation of solid-state batteries is provided.

[0359] In some embodiments of the various aspects of the present application, the solid-state battery may be a sulfide solid-state battery. The definition of sulfide solid-state battery can be found in the above text.

[0360] In some embodiments of the present invention, the solid-state battery may be a sulfide all-solid-state battery. The definition of a sulfide all-solid-state battery can be found in the above text.

[0361] In this application, the electrochemical performance of a battery, unless otherwise specified, generally includes at least the comprehensive performance in terms of discharge capacity and cycle performance.

[0362] A solid-state battery includes at least one solid-state battery cell. A solid-state battery may include one or more solid-state battery cells.

[0363] In this application, unless otherwise specified, a "solid-state battery cell" refers to a basic unit that can realize the mutual conversion of chemical energy and electrical energy, and its components are all solid. In some embodiments, the solid-state battery cell can be an all-solid-state battery cell.

[0364] Without limitation, a solid-state battery cell (which may be an all-solid-state battery cell) may include a positive electrode layer, a solid electrolyte layer, and a negative electrode layer, wherein the solid electrolyte layer is located between the positive electrode layer and the negative electrode layer. During the charge and discharge process of the battery, active ions are embedded and extracted back and forth between the positive electrode layer and the negative electrode layer. The solid electrolyte layer acts as an ion conductor between the positive electrode layer and the negative electrode layer, and can also isolate the positive electrode layer from the negative electrode layer to prevent short circuits between the positive and negative electrodes.

[0365] Unless otherwise specified, the positive electrode layer in the solid-state battery includes the positive electrode film described in the first aspect of the present application. It can be composed solely of the positive electrode film described in the first aspect of the present application, or it can be combined with other films suitable for the positive electrode to form a positive electrode layer.

[0366] The following is some description about the solid electrolyte layer.

[0367] The solid electrolyte layer plays the role of conducting ions between the positive electrode layer and the negative electrode layer, and can also isolate the positive electrode layer and the negative electrode layer to prevent the positive and negative electrodes from short-circuiting.

[0368] It is understood that the solid electrolyte layer includes a solid electrolyte. The solid electrolyte in the solid electrolyte layer can be a solid electrolyte known in the art that can be used in solid-state batteries.

[0369] The types of solid electrolytes present in different layers of a solid-state battery can be the same or different. For example, the solid electrolytes in the positive electrode electrolyte particles and the solid electrolyte layer can be the same or different.

[0370] As a non-limiting example, the positive electrode electrolyte particles and the solid electrolyte in the solid electrolyte layer can each independently include one or more of the following materials: one or more of a sulfide solid electrolyte, a halide solid electrolyte, an oxide solid electrolyte, a polymer solid electrolyte, etc. The type of sulfide solid electrolyte in the solid electrolyte layer can be the same as or different from the sulfide solid electrolyte in the positive electrode layer (such as the aforementioned positive electrode film). Taking a sulfide solid electrolyte as an example, a sulfide solid electrolyte refers to a solid electrolyte containing a sulfide electrolyte component, that is, a sulfide solid electrolyte is a sulfide-based electrolyte.

[0371] As another non-limiting example, the positive electrode electrolyte particles and the solid electrolyte in the solid electrolyte layer may each independently include but are not limited to one or more of an oxide solid electrolyte, a sulfide solid electrolyte and a halide solid electrolyte. In some of these embodiments, the positive electrode electrolyte particles and the solid electrolyte in the solid electrolyte layer may each independently include but are not limited to one or more of an Argyrodite-type sulfide electrolyte and a halide electrolyte. Among them, non-limiting examples of oxide solid electrolytes may include LISICON-type oxide electrolytes (such as γ-Li3PO4, etc.), NASICON-type oxide electrolytes (such as Li 1+x Al x Ge 2-x (PO4)3,Li 1+x Al x Ti 2-x (PO4)3, etc., 0≤x≤1), Garnet type (such as Li7La3Zr2O12, etc.), Perovskite type oxide electrolyte (such as Li 3x La 2 / 3-x TiO3, etc., 0≤x≤0.5) etc. Non-limiting examples of sulfide-based solid electrolytes may include Li 10 GeP2S 12 , Li2S-P2S5, Argyrodite type (such as Li6PS5Cl, Li 5.5 PS 5.5 Cl 1.5 Non-limiting examples of the halide-based solid electrolyte may include one or more of Li3InCl6, Li3YCl6, Li3ScCl6, Li3ErCl6, Li2ZrCl6, etc.

[0372] In some embodiments, the solid electrolyte layer may be pressed from a solid electrolyte material into a solid electrolyte membrane.

[0373] In some embodiments, the thickness of the solid electrolyte layer may be 0.1 μm to 1000 μm, and may be optionally 10 μm to 100 μm, 100 μm to 800 μm, 500 μm to 800 μm, or the like.

[0374] The following is some description about the negative electrode layer.

[0375] The negative electrode layer can be provided by a negative electrode sheet or negative electrode membrane that can be used in solid-state batteries in the art. Alternatively, the negative electrode layer component materials can be directly pressed onto one surface of the solid electrolyte layer to form a negative electrode membrane layer. The negative electrode membrane can be combined with other films suitable for the negative electrode to form a negative electrode sheet or negative electrode layer.

[0376] The negative electrode layer can be prepared by a dry process or a wet process. For example, a dry process can be used to form a film by pressing. Another example is a wet process can be used to form a film by coating.

[0377] The negative electrode layer includes a negative electrode active material layer. The negative electrode active material layer includes negative electrode active particles. The negative electrode active particles contain a negative electrode active material.

[0378] Without limitation, the weight percentage of the negative electrode active particles or the negative electrode active material in the negative electrode active material layer may be ≥80 wt %, and further may be ≥90 wt %.

[0379] In some embodiments, the negative electrode active particles or the negative electrode active material are lithium-indium alloy (InLi alloy).

[0380] In some embodiments, the negative electrode layer is an InLi alloy film.

[0381] In some embodiments, the negative electrode active material may also adopt a negative electrode active material that is well known in the art and can be used for solid-state batteries. As a non-limiting example, the negative electrode active material may include one or more of the following materials: elemental silicon, elemental tin, silicon-carbon negative electrode (silicon-carbon composite material), silicon monoxide, graphite, and one or more of metallic lithium. However, the present application is not limited to these materials or substances, and other traditional materials that can be used as battery negative electrode active materials can also be used. These negative electrode active materials can be used alone or in combination of two or more.

[0382] In some embodiments, the negative electrode sheet or negative electrode film may include a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector, the negative electrode active material layer including a negative electrode active material. As a non-limiting example, the negative electrode current collector has two surfaces that face away from each other in the thickness direction of the negative electrode current collector, and the negative electrode active material layer is disposed on either or both of the two facing surfaces of the negative electrode current collector. In some embodiments, the negative electrode current collector may be a metal foil or a composite current collector. For example, copper foil may be used as the metal foil. In the negative electrode current collector, the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer. In the negative electrode current collector, the composite current collector may be formed by forming a metal material on a polymer material base layer. Non-limiting examples of the metal material in the negative electrode current collector may include one or more of copper, copper alloys, nickel, nickel alloys, titanium, titanium alloys, silver, and silver alloys. In the negative electrode current collector, non-limiting examples of the polymer material substrate may include one or more of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), and the like.

[0383] In some embodiments, the negative electrode active material layer may optionally include a negative electrode conductive agent. Without limitation, the negative electrode conductive agent may include one or more of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers. Without limitation, the weight percentage of the negative electrode conductive agent in the negative electrode active material layer may be 0 to 15 wt %, further preferably 0 to 10 wt %, and even further preferably 0 to 5 wt %.

[0384] In some embodiments, the negative electrode active material layer may optionally include a binder (referred to as a negative electrode binder). As non-limiting examples, the negative electrode binder may include one or more of styrene-butadiene rubber (SBR), polyacrylic acids (PAAs), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS). Without limitation, the weight percentage of the negative electrode binder in the negative electrode active material layer may be 0-10 wt %, further 0-5 wt %, further 1 wt %-5 wt %, and further optionally 1 wt %-3 wt %.

[0385] In some embodiments, the negative electrode active material layer may optionally include other additives, such as a thickener (e.g., sodium carboxymethyl cellulose (CMC-Na)). The weight percentage of the other additives in the negative electrode active material layer may be 0-15 wt %, further preferably 0-10 wt %, further preferably 0-5 wt %, further preferably 0-3 wt %, and further preferably 0-2 wt %.

[0386] In some embodiments, the negative electrode sheet or negative electrode membrane can be prepared in the following manner: the components for preparing the negative electrode sheet or negative electrode membrane, such as negative electrode active particles, negative electrode conductive agent, binder (i.e., negative electrode binder) and any other components are dispersed in a solvent (a non-limiting example of the solvent is N-methylpyrrolidone (NMP)) to form a negative electrode slurry. Further, the negative electrode slurry is coated on at least one side of the negative electrode current collector, and after drying, cold pressing and other processes, the negative electrode sheet or negative electrode membrane can be obtained. The cold pressing can be performed using a cold rolling mill. The surface of the negative electrode current collector coated with the negative electrode slurry can be on a single surface of the negative electrode current collector or on both surfaces of the negative electrode current collector. The solid content of the negative electrode slurry can be 30wt% to 70wt%, and can optionally be 40wt% to 60wt%. The viscosity of the negative electrode slurry at room temperature can be adjusted to 2000mPa·s to 10000mPa·s, and can be optionally 3000mPa·s to 10000mPa·s. When applying the negative electrode slurry, the coating unit area density based on dry weight (excluding solvent) can be 75g / m 2 ~220g / m 2 The compaction density of the negative electrode sheet or negative electrode membrane can be 1.0g / cm 3 ~2.0g / cm 3 , optional 1.0g / cm 3 ~1.8g / cm 3 .

[0387] Without limitation, the positive electrode sheet, the solid electrolyte membrane and the negative electrode sheet may be stacked in sequence, the solid electrolyte membrane may be placed between the positive electrode sheet and the negative electrode sheet, and the solid-state battery cell may be prepared by hot rolling.

[0388] In a non-limiting manner, the positive electrode membrane, the solid electrolyte membrane and the negative electrode membrane may be stacked in sequence, the solid electrolyte membrane may be placed between the positive electrode membrane and the negative electrode membrane, and the solid-state battery cell may be prepared by hot rolling.

[0389] In some embodiments, the solid-state battery cell 5 includes a solid-state battery cell 52 .

[0390] In some embodiments, the solid-state battery cell is an all-solid-state battery cell.

[0391] In some embodiments, the solid-state battery cell 52 (which may be an all-solid-state battery cell) includes a positive electrode layer 200, a solid electrolyte layer 100, and a negative electrode layer 300 stacked in sequence, an example of which can be seen in Figure 15. Unless otherwise specified, the positive electrode layer 200 includes a positive electrode film 20.

[0392] In some embodiments, the solid-state battery cell 52 includes a positive electrode layer 200, a solid electrolyte layer 100, and a negative electrode layer 300 stacked in sequence. The positive electrode layer 200 includes a positive electrode film 20, which includes a positive electrode current collector 210 and positive electrode active material layers 220 located on both sides of the positive electrode current collector. The positive electrode active material layer 220 is disposed between the positive electrode current collector 210 and the solid electrolyte layer 100. An example of this is shown in FIG16 .

[0393] In some embodiments, the solid-state battery may include an outer packaging that can be used to encapsulate the solid-state battery cell.

[0394] In some embodiments, the outer packaging of the solid-state battery can be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc. The outer packaging of the solid-state battery can also be a soft package, such as a bag-type soft package. The material of the soft package can be plastic. Further, non-limiting examples of plastic can include one or more of polypropylene, polybutylene terephthalate, and polybutylene succinate.

[0395] The present application has no particular limitation on the shape of the solid-state battery cell, which can be cylindrical, square, or any other shape. For example, FIG17 shows a solid-state battery cell 5 with a square structure as an example.

[0396] In some embodiments, referring to Figure 18, the outer packaging may include a shell 51 and a cover plate 53. The shell 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose a receiving cavity. The shell 51 has an opening connected to the receiving cavity, and the cover plate 53 can be covered on the opening to close the receiving cavity. The solid-state battery cell 52 is encapsulated in the receiving cavity. The number of solid-state battery cells 52 contained in the solid-state battery cell 5 can be one or more, and those skilled in the art can select according to actual needs.

[0397] The solid-state battery can be a battery module 4 or a battery pack 1 .

[0398] The battery module includes at least one solid-state battery cell. The number of solid-state battery cells contained in the battery module can be one or more, and those skilled in the art can select an appropriate number based on the application and capacity of the battery module.

[0399] Figure 19 shows an example battery module 4. Referring to Figure 19 , within the battery module 4, multiple solid-state battery cells 5 can be arranged sequentially along the length of the battery module 4. Of course, they can also be arranged in any other manner. Furthermore, the multiple solid-state battery cells 5 can be secured using fasteners.

[0400] Optionally, the battery module 4 may further include a housing having a receiving space, and the plurality of solid-state battery cells 5 are received in the receiving space.

[0401] In some embodiments, the battery modules may be assembled into a battery pack. The battery pack may contain one or more battery modules. Those skilled in the art may select an appropriate number based on the application and capacity of the battery pack.

[0402] Figures 20 and 21 illustrate an example battery pack 1. Referring to Figures 20 and 21 , the battery pack 1 may include a battery box and multiple battery modules 4 disposed within the battery box. The battery box comprises an upper case 2 and a lower case 3. The upper case 2 can be placed over the lower case 3 to form an enclosed space for accommodating the battery modules 4. The multiple battery modules 4 can be arranged in any manner within the battery box.

[0403] In some embodiments, the electrical device includes the solid-state battery of any embodiment provided herein.

[0404] Without limitation, solid-state batteries can be used as power sources for electrical devices or as energy storage units for electrical devices. Electrical devices may include, but are not limited to, mobile devices, electric vehicles, electric trains, ships and satellites, energy storage systems, and the like. Examples of mobile devices include, but are not limited to, mobile phones and laptops; examples of electric vehicles include, but are not limited to, pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, electric motorcycles, and electric tools. The electrical device may also be used in fields such as military equipment and aerospace, and in energy storage power systems such as hydropower, thermal power, wind power, and solar power stations.

[0405] As an electrical device, a solid-state battery can be selected according to its usage requirements.

[0406] Figure 22 shows an example of an electric device 6. This device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle. To meet the high power and high energy density requirements of solid-state batteries, a battery pack or battery module can be used.

[0407] Another example device may be a mobile phone, a tablet computer, a laptop computer, etc. Such a device is usually required to be lightweight and thin, and may use a solid-state battery as a power source.

[0408] Below, some embodiments of the present application are described. The embodiment described below is exemplary, is only used to explain the present application, and cannot be construed as limiting the present application. In the embodiment, if no technology or conditions are indicated, it is carried out according to the description above, or according to the technology or conditions described in the document in this area, or according to the product specification. Reagents used or instruments that do not indicate manufacturers are conventional products that can be obtained commercially, or can be synthesized in a conventional manner by commercially available products.

[0409] Unless otherwise specified, in the following examples and comparative examples, raw materials with the same chemical formula are from the same synthesis batch or the same product number, or are prepared according to the same stoichiometric ratio and in accordance with the same method.

[0410] In the following examples, room temperature refers to 20°C to 30°C.

[0411] D v 50 tests:

[0412] In the following examples and comparative examples, the D values ​​of the positive electrode active particles, positive electrode electrolyte particles and oxygen storage particles are v 50 can be tested and confirmed by the following method: Equipment model: Malvern 2000 (MasterSizer 2000) laser particle size analyzer, reference standard process: GB / T19077-2016 / ISO 13320:2009, test process: take an appropriate amount of the sample to be tested (the sample concentration is guaranteed to be 8%-12% (w / v) shading), add 20mL of solvent (such as p-xylene or deionized water), and at the same time, ultraviolet for 5 minutes (53KHz / 120W) to ensure that the sample is completely dispersed, and then measure the sample according to GB / T19077-2016 / ISO 13320:2009 standard.

[0413] The D of the positive electrode active particles and electrolyte particles involved in the following examples v The recorded value of 50, unless otherwise specified, complies with the "rounding off" counting rule.

[0414] The transmission electron microscope (TEM) is a FEI / Talos F200X instrument with a test accelerating voltage of 200 kV. This instrument integrates high-resolution scanning / transmission electron microscopy (STEM) and TEM imaging capabilities, along with energy-dispersive X-ray spectroscopy (EDS) signal detection and three-dimensional chemical characterization based on compositional mapping.

[0415] XRD test instrument and parameters: D8 Advance Da Vinci X, Cu Kα1, 2θ scanning range of 20° to 110°, scanning speed of 5° / min.

[0416] In the following examples, unless otherwise specified, when the particle body is coated with oxygen storage material to obtain the target coated particle, the "coating amount of oxygen storage material" or "coating amount of oxygen storage layer" refers to the weight proportion of oxygen storage material in the target coated particle.

[0417] In the following examples, YBaCo4O7 (YBCO) is a yttrium barium cobalt oxide type oxygen storage material, La 0.8 Sr 0.2 CoO3 is a perovskite-type oxygen storage material, La2O2SO4 and Ce 0.6 Zr 0.3 Al 0.1 O 1.95 It is a lanthanide metal sulfate type oxygen storage material; NCM811 is a high nickel type lithium transition metal oxide, LiCoO2 is a lithium cobalt oxide type lithium transition metal oxide, Li 1.2 Mn 0.48 Ni 0.16 Co 0.16 O2 is a lithium-rich manganese-based lithium transition metal oxide.

[0418] In the following examples and comparative examples, unless otherwise specified, steps involving sulfide-based electrolyte materials were performed in an argon atmosphere.

[0419] It should be noted that sulfide all-solid-state batteries are used as non-limiting examples of solid-state batteries in the following embodiments and examples.

[0420] 1. Preparation Example

[0421] (1) Use coated positive electrode active particles

[0422] Example 1. Preparation of coated positive electrode active particles, positive electrode film, positive electrode layer and corresponding solid-state battery (a sulfide solid-state battery).

[0423] (1) Preparation of 2 wt% YBaCo4O7 (YBCO, oxygen storage material) coated LiNi 0.8 Co 0.1 Mn 0.1 O2 (NCM811 or NCM 811 , as the positive electrode active body) to obtain coated positive electrode active particles.

[0424] Y2O3, BaCO3 and Co3O4 are used as raw materials, weighed according to the stoichiometric ratio of the oxygen storage material, mixed and stirred in an organic solvent (ethanol) and ball-milled to make the raw materials uniformly dispersed. The ball-milled raw materials are dried at 80°C in a forced air drying oven and heat-treated at 1000°C for 12 hours in an air atmosphere. The sintered sample is ground and then heat-treated at 1100°C for 24 hours to obtain YBCO oxygen storage material.

[0425] The XRD pattern of the YBCO oxygen storage material prepared in this example can be seen in Figure 23.

[0426] The obtained YBCO oxygen storage material is ground into nano-sized (1nm~50nm) oxygen storage particles using a sand mill, and then the nano-sized YBCO oxygen storage particles and NCM811 are evenly mixed using a dry coating device. The coating amount of the oxygen storage material is 2wt%, and the obtained material is heat-treated at 450°C in an argon atmosphere for 5h to obtain coated positive electrode active particles, which have a 2wt% YBCO-coated NCM811 positive electrode material structure and can also be recorded as "2wt% YBaCo4O7-coated NCM811 positive electrode active particles" as a backup solid-state battery material.

[0427] Transmission electron microscopy (TEM) analysis shows that YBCO is well coated on the surface of the positive electrode material NCM811, with the surface coating (also known as the oxygen storage layer) being approximately 2 nm thick. See Figure 24.

[0428] (2) Preparation of positive electrode membrane (positive electrode membrane, used as positive electrode sheet of solid-state battery).

[0429] In an argon atmosphere, 2 wt% YBaCo4O7 was coated on the NCM811 positive electrode active particles (D v 50 is 4μm), Li6PS5Cl sulfide electrolyte (D v 50 is 1 μm), conductive agent VGCF (vapor grown carbon fiber) and binder polytetrafluoroethylene (PTFE) are weighed in a weight ratio of 85:13:1:1, and mixed evenly in a double planetary mixer. The evenly mixed powder is then heated and pressurized in an internal mixer to form a mass material, which is then hot-rolled at 80°C to form a self-supporting positive electrode sheet, and finally hot-rolled with the positive electrode current collector Al foil to obtain a positive electrode membrane.

[0430] (3) Preparation of solid electrolyte membranes (solid electrolyte membranes) and assembly of all-solid-state batteries.

[0431] In an argon atmosphere, 100 mg of sulfide electrolyte LPSCl was weighed, added to a battery mold, and pressurized to obtain a solid electrolyte membrane. Then, the positive electrode membrane was placed on one side of the solid electrolyte membrane, and InLi alloy was stacked on the other side as the negative electrode layer to assemble an all-solid-state battery. At this time, the solid electrolyte membrane was used as the solid electrolyte layer and the positive electrode membrane was used as the positive electrode layer.

[0432] The battery test window is 2.8~4.3V vs Li.

[0433] Example 2. Changing the amount of oxygen storage material coated in the positive electrode active particles

[0434] The coated positive electrode active material, positive electrode film, and all-solid-state battery were prepared using essentially the same method as in Example 1, except that the YBCO coating was 1 wt % and the oxygen storage layer was approximately 1 nm thick. The remaining steps were identical to those in Example 1. See Table 1 for details.

[0435] Example 3. Changing the coating amount of oxygen storage material in the coated positive electrode active particles

[0436] The coated positive electrode active material, positive electrode film, and all-solid-state battery were prepared using essentially the same method as in Example 1, except that the YBCO coating was 3 wt% and the oxygen storage layer had a thickness of approximately 3 nm to 4 nm. The remaining steps were identical to those in Example 1. See Table 1 for details.

[0437] Example 4. Changing the type and amount of oxygen storage material in the coated positive electrode active particles

[0438] The coated positive electrode active material, positive electrode film and all-solid-state battery were prepared by the same method as in Example 1, except that the coated positive electrode active particles were different and 1 wt% La 0.8 Sr 0.2 CoO3 coated LiNi 0.8 Co 0.1 Mn 0.1 The coated positive electrode active particles are obtained by coating with O2 (NCM811, positive electrode active body). See Table 1.

[0439] La(NO3)3·6H2O, Co(NO3)2·6H2O, Sr(NO3)2 and cetyltrimethylammonium bromide were added to deionized water in a stoichiometric ratio and stirred. The pH was then adjusted to 9 using ammonia water. After the raw materials were fully dissolved, NCM811 positive electrode active material (D v 50 is 4 μm), heated in an oil bath at 80°C with stirring until the solvent is completely evaporated, and the collected powder is heated at 500°C for 5h to obtain coated positive active particles having 1wt% La 0.8 Sr 0.2 CoO3 coated NCM811 structure can be expressed as “1wt%La 0.8 Sr 0.2 CoO3 coated NCM811".

[0440] According to TEM test results, the thickness of the surface coating layer (ie, the oxygen storage layer) is about 2 nm.

[0441] Example 5. Changing the type of oxygen storage material in the coated positive electrode active particles

[0442] The coated positive electrode active material, positive electrode film and all-solid-state battery were prepared by the same method as in Example 1, except that the coated positive electrode active particles were different and 2 wt% La2O2SO4 was used to coat LiNi 0.8 Co 0.1 Mn 0.1 The coated positive electrode active particles are obtained by coating with O2 (NCM811, positive electrode active body). See Table 1.

[0443] La(NO3)3·6H2O and sodium dodecylsulfonate CH3(CH2) 10 CH2SO3Na was added to deionized water according to the stoichiometric ratio, stirred, and ammonia was added to adjust the pH value to 9. After the raw materials were fully dissolved, LiNi was added. 0.8 Co 0.1 Mn 0.1 O2 positive electrode (D v 50 is 4 μm), heated in an oil bath at 80° C. with stirring until the solvent is completely evaporated, and the collected powder is heated at 550° C. for 5 h to obtain coated positive electrode active particles having a 2 wt% La2O2SO4-coated NCM811 structure.

[0444] According to TEM test results, the thickness of the surface coating layer (ie, the oxygen storage layer) is about 2 nm.

[0445] Examples 6-9. Changing the amount of oxygen storage material coated in the positive electrode active particles

[0446] The coated positive electrode active material, positive electrode film and all-solid-state battery were prepared by a method substantially the same as in Example 1, with the difference being that the coating amount of the oxygen storage material was different, as shown in Table 1.

[0447] Example 10-11. Changing the Type of Positive Electrode Active Material in Coated Positive Electrode Active Particles

[0448] The coated positive electrode active material, positive electrode film and all-solid-state battery were prepared by the same method as in Example 1, except that the types of positive electrode active materials in the coated positive electrode active particles were different. Example 10 used LiCoO2, and Example 11 used Li 1.2 Mn 0.48 Ni 0.16 Co 0.16 O2, please refer to Table 1.

[0449] Example 12-13. Changing the D of the coated positive electrode active particles v 50.

[0450] The coated positive electrode active material, positive electrode film and all-solid-state battery were prepared by the same method as in Example 1, except that the positive electrode active body with different particle sizes was used to prepare the positive electrode active body with different Dv 50% of the coated positive electrode active particles. Please refer to Table 1.

[0451] Example 14. Changing the amount of coated positive electrode active particles in the positive electrode active material layer.

[0452] The coated positive electrode active material, positive electrode film, and all-solid-state battery were prepared using a method substantially similar to that of Example 1, with the following differences: the amount of coated positive electrode active particles in the positive electrode active material layer was different. While the total weight proportion of the positive electrode active particles in the positive electrode active material layer remained unchanged, 15 wt% NCM811 was used instead of the coated positive electrode active particles in Example 1. That is, a mixture of coated positive electrode active particles (2 wt% YBaCo4O7 coated NCM811 positive electrode active particles) and positive electrode active particles without an oxygen storage layer (NCM811) was used as the positive electrode active particles. In the step of preparing the positive electrode film, the weight ratio of the coated positive electrode active particles, positive electrode active particles without an oxygen storage layer, conductive agent VGCF, and binder was 70:15:13:1:1. For details, see Table 1.

[0453] Comparative Example 1. The positive electrode active particles have no coating layer, including no oxygen storage layer.

[0454] The positive electrode film and the all-solid-state battery were prepared by the same method as in Example 1, except that the positive electrode active particles used were NCM811 positive electrode active materials without any surface coating. That is, in step (2), the positive electrode material (D v 50 is about 4μm) instead of 2wt% YBaCo4O7 coated NCM811 positive electrode active particles (D v 50 is 4μm).

[0455] Comparative Example 2-3. The positive electrode active particles are provided with a coating layer but no oxygen storage layer; a non-oxygen storage material is used instead of the oxygen storage material for coating.

[0456] Comparative Example 2 uses a method basically the same as Example 1 to prepare coated positive electrode active materials, positive electrode films and all-solid-state batteries, except that: the positive electrode active particles used are NCM811 positive electrode active materials coated with Li2ZrO3, and the thickness of the Li2ZrO3 coating layer is about 2nm.

[0457] Comparative Example 3 uses a method basically the same as Example 1 to prepare coated positive electrode active materials, positive electrode films and all-solid-state batteries, except that: the positive electrode active particles used are NCM811 positive electrode active materials coated with LiNbO3, and the thickness of the LiNbO3 coating layer is about 2nm.

[0458] Comparative Example 4: For the positive electrode active particles, the oxygen storage material is introduced by physical blending to replace the oxygen storage layer in the form of a coating layer.

[0459] Comparative Example 4 uses a method basically the same as Example 1 to prepare coated positive electrode active materials, positive electrode films and all-solid-state batteries, except that the step of preparing coated positive electrode active particles is omitted and the composition of the positive electrode film is different.

[0460] In Comparative Example 4, 0.2 g YBaCo4O7 (D v 50 (about 200 nm) and 10 g of NCM811 material were ground and mixed in a mortar to obtain NCM811 doped with oxygen storage materials. Then, NCM811 doped with oxygen storage materials was mixed with Li6PS5Cl sulfide electrolyte (D v 50 is 1 μm), a conductive agent VGCF (vapor grown carbon fiber) and a binder polytetrafluoroethylene (PTFE) are mixed in a weight ratio of 85:13:1:1, and mixed evenly in a double planetary mixer. The evenly mixed powder is then heated and pressurized in an internal mixer to form a mass material, and then hot-rolled at 80°C to form a self-supporting positive electrode sheet, and finally hot-rolled with the positive electrode current collector Al foil to obtain a positive electrode membrane.

[0461] Table 1. Related parameters of coated positive electrode active particles

[0462] (2) Using coated electrolyte particles

[0463] Example X1. Preparation of coated electrolyte particles (2wt% La2O2SO4 coated Li 5.5 PS 4.5 Cl 1.5 sulfide electrolyte), solid electrolyte membrane and corresponding all-solid-state batteries.

[0464] (1) Preparation of coated electrolyte particles.

[0465] La(NO3)3·6H2O, sodium dodecylsulfonate CH3(CH2) 10 A solution of CH2SO3Na, ammonia, and deionized water in a molar ratio of 2:1:30:60 was prepared and placed in a 40°C constant-temperature water bath for 1 hour. The temperature was then raised to 50°C and stirred continuously for 10 hours. The pH of the solution was adjusted to 9. The solution was then filtered, washed until neutral, and finally heat-treated at 550°C in air for 5 hours to produce a crude La2O2SO4 material. The resulting La2O2SO4 material was further ground using a sand mill to produce nanometer-sized (1nm-50nm) oxygen storage particles, which served as the La2O2SO4 oxygen storage material for the subsequent coating step.

[0466] In an argon atmosphere protected glove box, weigh 0.2g of the above-synthesized nano La2O2SO4 oxygen storage material into a glass beaker, add an appropriate amount of p-xylene solvent, stir thoroughly to obtain a glue solution, and then add 10g Li 5.5 PS 4.5 Cl 1.5 Sulfide solid electrolyte (D v 50 is about 1 μm), continue stirring for 3 hours, then put it into a vacuum oven and dry it in vacuum at 120℃ for 10 hours to obtain coated electrolyte particles, which can be recorded as 2wt% La2O2SO4 coated Li 5.5 PS 4.5 Cl 1.5 Sulfide electrolyte.

[0467] According to TEM test analysis results, the thickness of the obtained coating layer (oxygen storage layer) is about 2 nm.

[0468] (2) Prepare the positive electrode membrane.

[0469] In an argon atmosphere, LiNi 0.8 Co 0.1 Mn 0.1 O2(NCM811) positive electrode active particles (D v 50 is 4 μm), coated electrolyte particles (previously prepared 2 wt% La2O2SO4 coated Li 5.5 PS 4.5 Cl 1.5 The raw materials (sulfide electrolyte), conductive agent VGCF (vapor-grown carbon fiber) and binder polytetrafluoroethylene (PTFE) were weighed in a weight ratio of 85:13:1:1 and mixed evenly in a double planetary mixer. The evenly mixed powder was then heated and pressurized in an internal mixer to form a mass material, which was then hot-rolled at 80°C to form a self-supporting positive electrode sheet. Finally, it was hot-rolled with the positive electrode current collector Al foil to obtain a positive electrode membrane.

[0470] (3) In an argon atmosphere, weigh 100 mg of sulfide electrolyte Li 5.5 PS 4.5 Cl 1.5 , added to the battery mold and pressurized to obtain a solid electrolyte membrane, and then the positive electrode membrane is placed on one side of the solid electrolyte membrane, and InLi alloy is stacked on the other side as the negative electrode layer to assemble an all-solid-state battery.

[0471] Example X2. Coated electrolyte particles are 2 wt% YBaCo4O7 coated Li 5.5 PS 4.5 Cl 1.5 Sulfide electrolyte.

[0472] The positive electrode membrane and the all-solid-state battery were prepared by the same method as in Example X1. The difference was that the coating electrolyte particles used in the preparation of the positive electrode membrane were different. The coating electrolyte particles used in this example were 2 wt% YBaCo4O7 coated Li 5.5 PS 4.5 Cl 1.5 Sulfide electrolyte.

[0473] (1) Y2O3, BaCO3, and Co3O4 were weighed according to the stoichiometric ratio and mixed in an organic solvent (ethanol) by ball milling to uniformly disperse the raw materials. The ball-milled raw materials were dried at 80°C in a forced air drying oven and then heat-treated at 1000°C for 12 h in air. The sintered sample was ground and then heat-treated at 1100°C for 24 h to obtain the desired YBaCo4O7 coarse material. The obtained YBaCo4O7 coarse material was further ground into nano-sized (1 nm to 50 nm) oxygen storage particles using a sand mill and used as YBaCo4O7 oxygen storage material for the subsequent coating step.

[0474] In an argon atmosphere protected glove box, weigh 0.2g of the above synthesized nano YBaCo4O7 oxygen storage material into a glass beaker, add an appropriate amount of p-xylene solvent, stir thoroughly to obtain a glue solution, and then add 10g Li 5.5 PS 4.5 Cl 1.5 Sulfide solid electrolyte (D v 50 is about 1 μm), continue stirring for 3 hours, then put it into a vacuum oven and dry it in vacuum at 120℃ for 10 hours to obtain coated electrolyte particles, which can be recorded as 2wt% YBaCo4O7 coated Li 5.5 PS 4.5 Cl 1.5 Sulfide electrolyte.

[0475] According to TEM test analysis results, the thickness of the obtained coating layer (oxygen storage layer) is about 2 nm.

[0476] Example X3. Coated electrolyte particles are 1 wt% La 0.8 Sr 0.2 CoO3 coated Li 5.5 PS 4.5 Cl 1.5 Sulfide electrolyte.

[0477] The positive electrode membrane and the all-solid-state battery were prepared by the same method as in Example X1. The difference was that the coating electrolyte particles used in the preparation of the positive electrode membrane were different. The coating electrolyte particles used in this example were 1 wt% La 0.8 Sr 0.2 CoO3 coated Li 5.5 PS 4.5Cl 1.5 Sulfide electrolyte.

[0478] (1) La(NO3)3·6H2O, Co(NO3)2·6H2O, and Sr(NO3)2 were weighed in deionized water according to the stoichiometric ratio, and then La 0.8 Sr 0.2 The molar ratio of CoO3 to urea is 1:4, and urea is added to form a composite solution. The solution is placed in a water bath at 80°C and stirred continuously, and then ammonia water is added dropwise to adjust the pH of the solution to 9. The obtained precipitate is filtered and washed to neutrality. The obtained powder is sintered at 700°C in an air atmosphere for 5 hours, the sintered sample is ground, and then sintered at 1050°C for 10 hours to obtain the required La 0.8 Sr 0.2 CoO3 oxygen storage material. 0.8 Sr 0.2 CoO3 is further ground into nano-sized (1nm-50nm) oxygen storage particles using a sand mill, and used as Li 5.5 PS 4.5 Cl 1.5 The oxygen storage material is used for subsequent coating.

[0479] In an argon atmosphere protected glove box, weigh 0.1 g of the above synthesized nano La 0.8 Sr 0.2 CoO3 oxygen storage material was placed in a glass beaker, and an appropriate amount of p-xylene solvent was added and stirred thoroughly to obtain a glue solution. Then 10g Li 5.5 PS 4.5 Cl 1.5 Sulfide solid electrolyte (D v 50 is about 1 μm), continue stirring for 3 hours, then put it into a vacuum oven and dry it in vacuum at 120℃ for 10 hours to obtain coated electrolyte particles, which can be recorded as 1wt% La 0.8 Sr 0.2 CoO3 coated Li 5.5 PS 4.5 Cl 1.5 Sulfide electrolyte.

[0480] According to TEM test analysis results, the thickness of the obtained coating layer (oxygen storage layer) is about 2 nm.

[0481] Example X4. Coated electrolyte particles are 1 wt% Ce 0.6 Zr 0.3 Al 0.1 O 1.95 Coated Li 5.5 PS 4.5 Cl 1.5 Sulfide electrolyte.

[0482] The positive electrode membrane and the all-solid-state battery were prepared by the same method as in Example X1. The difference was that the coating electrolyte particles used in the preparation of the positive electrode membrane were different. The coating electrolyte particles used in this example were 1 wt% Ce. 0.6 Zr 0.3 Al 0.1 O 1.95 Coated Li 5.5 PS 4.5 Cl 1.5 Sulfide electrolyte.

[0483] (1) Cerium nitrate, zirconium nitrate and aluminum nitrate were weighed in stoichiometric ratio and added to deionized water, and then Ce 0.6 Zr 0.3 Al 0.1 O 1.95 Urea was added in a molar ratio of 1:4 to urea to prepare a composite solution. The solution was placed in a water bath at 80°C and stirred continuously, and then ammonia was added dropwise to adjust the pH of the solution to 9. The obtained precipitate was filtered and washed to neutrality. The obtained powder was sintered at 500°C in an air atmosphere for 5 hours, the sintered sample was ground, and then sintered at 1000°C for 10 hours to obtain Ce 0.6 Zr 0.3 Al 0.1 O 1.95 The obtained Ce 0.6 Zr 0.3 Al 0.1 O 1.95 The coarse material is further ground into nano-sized (1nm-50nm) oxygen storage particles using a sand mill as Li 5.5 PS 4.5 Cl 1.5 The oxygen storage material is used for subsequent coating.

[0484] In a glove box protected by argon atmosphere, 0.1 g of the above synthesized nano-Ce was weighed. 0.6 Zr 0.3 Al 0.1 O 1.95 The oxygen storage material was placed in a glass beaker, and an appropriate amount of p-xylene solvent was added. The mixture was stirred thoroughly to obtain a glue solution, and then 10g Li 5.5 PS 4.5 Cl 1.5 Sulfide solid electrolyte (D v 50 is about 1 μm), continue stirring for 3 hours, then put it into a vacuum oven and dry it in vacuum at 120℃ for 10 hours to obtain coated electrolyte particles, which can be recorded as 1wt% Ce 0.6 Zr 0.3 Al 0.1 O 1.95 Coated Li5.5 PS 4.5 Cl 1.5 Sulfide electrolyte.

[0485] According to TEM test analysis results, the thickness of the obtained coating layer (oxygen storage layer) is about 2 nm.

[0486] Examples X5 to X8. Changing the amount of oxygen storage material coated in the coated electrolyte particles

[0487] The coated electrolyte particles, positive electrode membrane and all-solid-state battery were prepared by a method basically the same as that in Example X1, except that the coating amount of the oxygen storage material in the coated electrolyte particles was different, as shown in Table 2.

[0488] Examples X9-X10. Changing the Type of Sulfide Electrolyte in the Coated Electrolyte Particles

[0489] The coated electrolyte particles, positive electrode membrane and all-solid-state battery were prepared by the same method as in Example X1, except that the types of sulfide electrolytes in the coated electrolyte particles were different. Example X9 used LGPS sulfide electrolyte Li 10 GeP2S 12 Example X10 uses 75Li2S-25P2S5, that is, a lithium sulfide pentasulfide diphosphorus complex sulfide electrolyte (75Li2S)·(25P2S5), which can be seen in Table 2.

[0490] Examples X11-X12. Changing the D of the coated electrolyte particles v 50.

[0491] The coated electrolyte particles, positive electrode membrane and all-solid-state battery were prepared by the same method as in Example X1, except that sulfide electrolyte materials with different particle sizes were used to prepare the electrolyte particles with different D v 50% coated electrolyte particles. See Table 2.

[0492] Example X13. Changing the amount of coated electrolyte particles in the positive electrode active material layer.

[0493] The coated electrolyte particles, the positive electrode membrane and the all-solid-state battery were prepared by the same method as in Example X1, except that the amount of the coated electrolyte particles in the positive electrode active material layer was different. When the total weight proportion of the positive electrode electrolyte particles in the positive electrode active material layer remained unchanged, 8 wt% of Li 5.5 PS 4.5 Cl 1.5 Sulfide solid electrolyte replaces the coated electrolyte particles in Example X1, that is, coated electrolyte particles (2wt% La2O2SO4 coated Li 5.5 PS 4.5Cl 1.5 Sulfide electrolyte) and sulfide-based electrolyte without oxygen storage layer (Li 5.5 PS 4.5 Cl 1.5 ) as the positive electrode electrolyte particles; in the step of preparing the positive electrode membrane, the weight ratio of the positive electrode active particles, the coated electrolyte particles, the sulfide-based electrolyte without an oxygen storage layer, the conductive agent VGCF, and the binder is 85:5:8:1:1. See Table 2.

[0494] Example X14. Both the positive electrode layer and the solid electrolyte layer use coated electrolyte particles to provide a solid electrolyte

[0495] The coated electrolyte particles, positive electrode membrane, solid electrolyte membrane and all-solid-state battery were prepared by the same method as in Example X1, except that the composition of the solid electrolyte membrane was different, and the coated electrolyte particles in Example X1 (2 wt% La2O2SO4 coated Li 5.5 PS 4.5 Cl 1.5 sulfide electrolyte) instead of Li 5.5 PS 4.5 Cl 1.5 Please refer to Table 2.

[0496] In an argon atmosphere, 100 mg of coated electrolyte particles (2 wt% La2O2SO4 coated Li 5.5 PS 4.5 Cl 1.5 sulfide electrolyte), added to a battery mold, pressurized to obtain a solid electrolyte membrane, and then the positive electrode membrane prepared by the same method as in Example X1 was placed on one side of the solid electrolyte membrane, and InLi alloy was stacked on the other side as a negative electrode layer to assemble an all-solid-state battery.

[0497] Example X15. The positive electrode layer includes coated positive electrode active particles and coated electrolyte particles.

[0498] The coated electrolyte particles, the positive electrode membrane and the all-solid-state battery were prepared by the method basically the same as that in Example X1, except that the composition of the positive electrode membrane was different, and the coated positive electrode active particles (2 wt% YBaCo4O7 coated NCM811 positive electrode active particles) prepared by the same method as in Example 1 were used to replace the positive electrode active particle raw material (NCM811) in the positive electrode membrane of Example X1; that is, the coated sulfide electrolyte (2 wt% La2O2SO4 coated Li 5.5 PS 4.5 Cl 1.5sulfide electrolyte) as the positive electrode electrolyte particles, and coated positive electrode active particles (2 wt% YBaCo4O7 coated NCM811 positive electrode active particles) prepared in the same manner as in Example 1 were used as the positive electrode active particles. When preparing the positive electrode membrane, the weight ratio of positive electrode active particles, positive electrode electrolyte particles, conductive agent, and binder remained at 85:13:1:1. See Table 2 for details.

[0499] Example X16. The positive electrode layer includes coated positive electrode active particles and coated electrolyte particles, and the solid electrolyte layer includes coated electrolyte particles.

[0500] The coated electrolyte particles, cathode membrane, solid electrolyte membrane, and all-solid-state battery were prepared using methods substantially identical to those of Example X1, with the difference being that the cathode membrane and solid electrolyte membrane had different compositions. See Table 2.

[0501] (1) The composition of the positive electrode membrane is different. The positive electrode active particles (2 wt% YBaCo4O7 coated NCM811 positive electrode active particles) prepared by the same method as in Example 1 are used to replace the positive electrode active particle raw material (NCM811) in the positive electrode membrane of Example X1; that is, the coated sulfide electrolyte (2 wt% La2O2SO4 coated Li 5.5 PS 4.5 Cl 1.5 The positive electrode active particles were prepared using the same method as in Example 1 (2 wt% YBaCo4O7 coated NCM811 positive electrode active particles). When preparing the positive electrode film, the weight ratio of the positive electrode active particles, positive electrode electrolyte particles, conductive agent, and binder was still 85:13:1:1.

[0502] (2) The composition of the solid electrolyte membrane is different. The coated electrolyte particles (2 wt% La2O2SO4 coated Li 5.5 PS 4.5 Cl 1.5 sulfide electrolyte) instead of Li 5.5 PS 4.5 Cl 1.5 .

[0503] In an argon atmosphere, 100 mg of coated electrolyte particles (2 wt% La2O2SO4 coated Li 5.5 PS 4.5 Cl 1.5 Sulfide electrolyte), added to the battery mold, pressurized to obtain a solid electrolyte membrane, and then placed the positive electrode membrane prepared in this example on one side of the solid electrolyte membrane, and stacked InLi alloy as the negative electrode layer on the other side to assemble into an all-solid-state battery.

[0504] Comparative Example X1: The positive electrode electrolyte particles do not have any coating layer, that is, no oxygen storage layer.

[0505] The positive electrode membrane and the all-solid-state battery were prepared by the same method as in Example X1, except that the positive electrode electrolyte particles used in the preparation of the positive electrode membrane were different. The positive electrode electrolyte particles in this example were Li-ion without any surface coating. 5.5 PS 4.5 Cl 1.5 Sulfide electrolyte.

[0506] Comparative Examples X2-X3. The positive electrode electrolyte particles are provided with a coating layer but no oxygen storage layer; a non-oxygen storage material is used instead of the oxygen storage material for coating.

[0507] Comparative Example X2 uses the same method as Example X1 to prepare the positive electrode membrane and the all-solid-state battery, except that the positive electrode electrolyte particles used are 2wt% La2O2SO4-coated LGPS sulfide electrolyte Li 10 GeP2S 12 The thickness of the La2O2SO4 coating layer is about 2nm. The positive electrode electrolyte particles can be recorded as "2wt% La2O2SO4 coated Li 10 GeP2S 12 ”.

[0508] Comparative Example X3 used essentially the same method as Example X1 to prepare a positive electrode membrane and an all-solid-state battery, except that the positive electrode electrolyte particles used were 75Li2S-25P2S5, a lithium sulfide phosphorus pentasulfide complex sulfide electrolyte coated with 2 wt% La2O2SO4. The La2O2SO4 coating layer had a thickness of approximately 2 nm. The positive electrode electrolyte particles can be referred to as "2 wt% La2O2SO4-coated 75Li2S-25P2S5."

[0509] Comparative Example X4: For the solid electrolyte material, an oxygen storage material is introduced by physical blending to replace the oxygen storage layer in the form of a coating layer.

[0510] Comparative Example X4 uses a method basically the same as Example X1 to prepare a positive electrode membrane and an all-solid-state battery, except that: the step of preparing the coated electrolyte particles is omitted, and the composition of the positive electrode membrane is different.

[0511] In comparative example X4, 0.2 g of La2O2SO4 (D v 50 about 200nm) and 10g of Li 5.5 PS 4.5 Cl 1.5 Sulfide solid electrolyte was ground and mixed in a mortar to obtain La2O2SO4 co-doped Li 5.5 PS4.5 Cl 1.5 Electrolyte material. Then LiNi 0.8 Co 0.1 Mn 0.1 O2(NCM811) positive electrode active particles (D v 50 is 4 μm), positive electrode electrolyte particles (La2O2SO4 mixed doped Li 5.5 PS 4.5 Cl 1.5 The raw materials (electrolyte material), conductive agent VGCF and binder PTFE) were weighed in a weight ratio of 85:13:1:1, and mixed evenly in a double planetary mixer. The evenly mixed powder was then heated and pressurized in an internal mixer to form a mass material, which was then hot-rolled at 80°C to form a self-supporting positive electrode sheet. Finally, it was hot-rolled with the positive electrode current collector Al foil to obtain a positive electrode membrane.

[0512] Table 2. Related parameters of coated electrolyte particles

[0513] In Table 2, the positive active particles of the positive electrode layers of Examples X1 to X14 are all NCM811 without an oxygen storage layer; the solid electrolyte layers of Examples X14 and X16 are 2 wt% La2O2SO4 coated Li 5.5 PS 4.5 Cl 1.5 The solid electrolyte layer in the other embodiments adopts Li 5.5 PS 4.5 Cl 1.5 .

[0514] 2. Test Method

[0515] The electrochemical performance of the positive electrode and the corresponding all-solid-state battery was tested using a solid-state mold battery, and the battery test window was 2.8V to 4.3V (relative to lithium potential).

[0516] 1. H2S release test of solid electrolyte materials

[0517] In a -55°C dew point environment, 100mg of electrolyte powder was evenly spread on a 5cm diameter culture dish. The culture dish containing the electrolyte powder was then placed in a 50L box through a sealed transfer box. The sealed transfer box containing the electrolyte powder culture dish was quickly opened in the box and the 50L box was sealed. A hydrogen sulfide sensor (PGM-2500) was placed in the box to record the cumulative value of hydrogen sulfide in the 50L box in real time. The reaction continued until the detection value of the hydrogen sulfide sensor no longer increased, indicating that the electrolyte had completely reacted with the water molecules in the box. At the same time, a fan with a blade diameter of 8cm was placed in the box. Since the density of hydrogen sulfide is greater than that of air, the fan can prevent the hydrogen sulfide gas from settling and make the hydrogen sulfide gas in the 50L box evenly distributed, ensuring the reliability of the hydrogen sulfide gas concentration test. Before the test, the 50L box was in an environment with a relative humidity of 70% RH.

[0518] Please refer to “Ionic conductivity of coated electrolyte particles” in Table 4.

[0519] 2. Ionic conductivity test of solid electrolyte materials

[0520] The ionic conductivity was measured by electrochemical impedance spectroscopy (EIS). The detailed process is as follows: 120 mg of solid electrolyte powder was poured into a 10 mm diameter tablet mold and pressed into a dense disc at 360 MPa. Then, a 10 mm diameter cylindrical stainless steel current collector was used to clamp the solid electrolyte membrane in the mold at 120 MPa. The current collector was then connected to an electrochemical workstation and tested at a bias voltage of 10 mV and a frequency range of 10 6 Electrochemical impedance spectroscopy (EIS) is performed on solid electrolyte membranes in the range of Hz to 10Hz. The intersection of the curve from the high frequency band to the low frequency band in the electrochemical impedance spectrum and the Z' axis is recorded as the resistance value R. The ionic conductivity can be calculated using formula (1):

[0521] Where d is the thickness of the solid electrolyte membrane, and A is the contact area between the solid electrolyte membrane and the current collector.

[0522] Please refer to “H2S release of coated electrolyte particles” in Table 4.

[0523] 3. First discharge capacity

[0524] The test process is as follows: the assembled all-solid-state battery is charged to 3.68V (4.3V vs. lithium) at a current density of 0.1C, allowed to rest for 10 minutes, and then discharged to 2.18V (2.8V vs. lithium) at a current density of 0.1C to obtain the battery's initial discharge capacity. The battery is tested at 25±3°C, where 1C = 200mA / g.

[0525] This can be included in the “0.1C discharge specific capacity” in Table 3 and the “first discharge capacity” in Table 4.

[0526] 4. First Coulombic efficiency

[0527] The first coulombic efficiency of the battery can be obtained by dividing the first discharge capacity obtained by the first charge capacity tested at 0.1C.

[0528] 5. Rate performance

[0529] The test process is as follows: the charge rate of the all-solid-state battery is fixed at 0.1C, and then discharged at the rates of 0.1C, 0.33C, 1C, 2C, and 3C, respectively. Each rate is cycled 3 times. The battery voltage test window is 2.8~4.3V vs.Li + / Li, the battery was tested at 25±3°C, where 1C=200mA / g.

[0530] 6. Cycle performance

[0531] The assembled all-solid-state battery was first charged and discharged for 3 cycles at a current density of 0.1C to obtain the initial discharge capacity and initial coulombic efficiency. Then, a long cycle test was performed at a current density of 0.33C for 200 cycles to calculate the battery's cycle capacity retention rate. The battery's voltage test window is 2.8-4.3V vs. Li + / Li, the battery was tested at 25±3°C, where 1C=200mA / g.

[0532] 3. Test Analysis Results

[0533] The test results can be found in Table 3.

[0534] In Examples 1 to 14, the positive electrode layers all include coated positive electrode active particles, in Examples X1 to X13, the positive electrode layers all include coated electrolyte particles, in Example X14, the positive electrode layer and the solid electrolyte layer all include coated electrolyte particles, in Example X15, the positive electrode layer includes coated positive electrode active particles and coated electrolyte particles, in Example X16, the positive electrode layer includes coated positive electrode active particles and coated electrolyte particles, and the solid electrolyte layer also includes coated electrolyte particles. The solid-state batteries prepared in each example have good discharge capacity and cycle performance, and further have good rate performance, and further have good first coulomb efficiency. It can be seen that coating at least one of the positive electrode active particles or the sulfide-based electrolyte with an oxygen storage material can improve the electrochemical properties of the sulfide solid-state battery, such as discharge capacity, rate performance, and cycle performance.

[0535] The experimental results of Examples X1 to X16 show that coating sulfide-based electrolytes with oxygen storage materials significantly reduces hydrogen sulfide release, significantly improves air stability, and simultaneously maintains good ionic conductivity. Sulfide solid-state batteries fabricated with these coated electrolyte particles exhibit excellent discharge capacity and cycle performance, as well as good rate capability and initial coulombic efficiency.

[0536] In addition, the battery voltage test window is 2.8 ~ 4.3V vs.Li + / Li, it can be seen that the stability of sulfide solid-state batteries at high voltage operation is significantly improved.

[0537] Compared with Examples 1-9, the positive electrode active particles of Comparative Example 1 are not provided with an oxygen storage layer. The discharge capacity, first coulombic efficiency, rate performance and cycle capacity retention rate of the sulfide solid-state battery of Comparative Example 1 are significantly deteriorated, and the cycle performance deterioration is very serious.

[0538] Compared with Example 1, the positive electrode active particles of Comparative Examples 2-3 were coated with non-oxygen storage materials, and the discharge capacity, first coulombic efficiency, rate performance and cycle capacity retention rate all deteriorated to varying degrees.

[0539] Compared with Example 1, the positive electrode layer of Comparative Example 4 uses positive electrode active particles of mixed doped oxygen storage materials, and the discharge capacity, first coulombic efficiency, rate performance and cycle capacity retention rate all deteriorate to varying degrees.

[0540] Compared with Examples X1-X8, the positive electrode electrolyte particles of Comparative Example X1 are not provided with an oxygen storage layer, and the amount of hydrogen sulfide released is significantly increased. The discharge capacity, first coulombic efficiency and cycle capacity retention rate of the sulfide solid-state battery of Comparative Example X1 are significantly deteriorated, and the cycle performance deteriorates very seriously.

[0541] Compared with Example X1, the positive electrode electrolyte particles of Comparative Examples X2-X3 are coated with non-oxygen storage materials, the hydrogen sulfide release is significantly increased, and the first discharge capacity, first coulombic efficiency and cycle capacity retention rate all deteriorate to varying degrees.

[0542] Compared with Example X1, the positive electrode layer of Comparative Example X4 uses positive electrode electrolyte particles that are co-doped with oxygen storage materials, and the hydrogen sulfide release amount is significantly increased, and the first discharge capacity, first coulombic efficiency and cycle capacity retention rate all deteriorate to varying degrees.

[0543] Table 3. Test results of Examples 1-14 and Comparative Examples 1-4

[0544] Table 4. Test results of Examples X1-X16 and Comparative Examples X1-X4

[0545] In addition, using coated electrolyte particles (such as the coated electrolyte particles in Example X1) in the solid electrolyte layer and using positive electrode active particles with a conventional coating structure and positive electrode electrolyte particles not coated with oxygen storage materials in the positive electrode layer can also improve the electrochemical properties of the solid-state battery, such as rate performance and cycle performance.

[0546] The description of each embodiment above tends to emphasize the differences between the embodiments, and the same or similar aspects can be referenced to each other. For the sake of brevity, this article will not go into details. The technical features of the embodiments described above can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification. It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples. Within the scope of the technical solution of this application, embodiments with essentially the same composition as the technical idea and the same effect are included in the technical scope of this application. The embodiments described above only express several embodiments of the present application, and the description is relatively detailed, but it cannot be understood as a limitation on the scope of the patent. In addition, without departing from the scope of the main purpose of this application, other methods of applying various modifications that can be thought of by those skilled in the art to the embodiments and combining some of the constituent elements in the embodiments are also included in the scope of this application.

Claims

1. A solid-state battery material comprising a coated particle, wherein the coated particle comprises a particle body and an oxygen storage layer located on at least a portion of a surface of the particle body, wherein the oxygen storage layer comprises an oxygen storage material; in, The coated particles are at least one of coated positive electrode active particles and coated electrolyte particles; When the coated particles are the coated positive electrode active particles, the particle body is a positive electrode active body, and the positive electrode active body contains a positive electrode active material; When the coated particles are the coated electrolyte particles, the particle body is a solid electrolyte body, and the solid electrolyte body contains a sulfide electrolyte.

2. The solid-state battery material according to claim 1, wherein The oxygen storage material includes one or more of a lanthanide metal oxysulfate type oxygen storage material, a yttrium barium cobalt oxide type oxygen storage material and a perovskite type oxygen storage material.

3. The solid-state battery material according to claim 2, wherein: The oxygen storage material meets one or more of the following characteristics: The lanthanide metal oxysulfate type oxygen storage material includes a chemical formula of Ln2O2SO 4-δ1 Oxygen storage material, wherein Ln is a lanthanide metal element, the lanthanide metal element includes one or more elements of La, Ce, Pr, Nd, Sm, Eu, Gd and Tb, 0≤δ1≤4; The yttrium barium cobalt oxide type oxygen storage material includes a chemical formula of (Y x M1 (1-x) )(Ba y M2 (1-y) )(Co z M3 (1-z) )4O 7+δ2 Oxygen storage material, wherein M1 is selected from one or more elements of Ca, In, Dy, Ho, Er, Tm, Yb and Lu, M2 is Sr, M3 is selected from one or more elements of Mn, Fe, Ni, Cu, Zn, Al, Ga and Zr, 0≤x≤1, 0≤y≤1, 0≤z≤1, 0≤δ2≤1.5; The perovskite oxygen storage material includes a chemical formula of La 1-a A a Mn 1-b B b O 3-δ3 Oxygen storage material, wherein A is selected from one or more elements of Sr, Y, Ce, Pr and Nd, B is selected from one or more elements of Ni, Fe, Cu and Co, 0≤a≤1, 0≤b≤1, 0≤δ3≤1.

4. The solid-state battery material according to any one of claims 1 to 3, wherein The weight proportion of the oxygen storage material in the coated particles is 0.1 wt% to 10 wt%, and can be optionally 0.5 wt% to 5 wt%.

5. The solid-state battery material according to any one of claims 1 to 4, wherein The thickness of the oxygen storage layer is 0.1 nm to 50 nm, and can be optionally 0.5 nm to 10 nm.

6. The solid-state battery material according to any one of claims 1 to 5, wherein The oxygen storage material includes oxygen storage particles; the particle size of the oxygen storage particles is 1nm to 100nm.

7. The solid-state battery material according to claim 6, wherein: The particle size of the oxygen storage particles is 1 nm to 50 nm. 8 . The solid-state battery material according to claim 1 , wherein the particle size of the positive electrode active body is 0.1 μm to 20 μm, and can be optionally 1 μm to 10 μm.

9. The solid-state battery material according to claim 8, wherein The D coating of the positive electrode active particles v 50 is 0.1μm~20μm, and can be selected as 1μm~10μm; among them, D v 50 represents the particle size corresponding to when the cumulative volume distribution percentage of the multi-particle mixture reaches 50%.

10. The solid-state battery material according to any one of claims 1 to 9, wherein The positive electrode active material includes an oxide positive electrode active material; Optionally, the oxide positive electrode active material includes lithium transition metal oxide.

11. The solid-state battery material according to claim 10, wherein: The lithium transition metal oxide includes one or more of a lithium cobalt oxide positive electrode active material, a high nickel positive electrode active material, a lithium-rich manganese-based positive electrode active material, and a modified form of any of the foregoing positive electrode active materials; the modified form includes one or more of a doping modification and a coating modification; Optionally, The lithium cobalt oxide type positive electrode active material comprises Li, Co and O, wherein the atomic molar ratio of Co to O is x2:2, and satisfies 0.9≤x2≤1; alternatively, the lithium cobalt oxide type positive electrode active material comprises Li, Co and O in an atomic molar ratio of 1:x2:2, and satisfies 0.9≤x2≤1; The high-nickel positive electrode active material comprises Li, Ni and O, wherein the atomic molar ratio of Ni to O is y2:2, and satisfies 0.6≤y2≤1; alternatively, the high-nickel positive electrode active material comprises Li, Ni and O in an atomic molar ratio of 1:y2:2, and satisfies 0.6≤y2≤1; The lithium-rich manganese-based positive electrode active material comprises Li, Mn and O elements in an atomic molar ratio of (1+p): (p+r(1-p)): (2+p), and satisfies 0 <p≤1,0≤r≤1。 12. The solid-state battery material according to claim 11, wherein The lithium transition metal oxide satisfies one or more of the following characteristics: 0.8≤y2≤1; 0.2≤p≤1.

13. The solid-state battery material according to claim 11 or 12, wherein: The lithium transition metal oxide satisfies one or more of the following characteristics: The lithium cobalt oxide positive electrode active material includes a chemical formula of LiCo x2 R 1-x2 O2 lithium transition metal oxide, R is selected from one or more elements of Ni, Mg, Ti, Al, Cr, Fe, Nb and Ta; The high nickel positive electrode active material includes a chemical formula of LiNi y2 Co z2 D 1-y2-z2 A lithium transition metal oxide of O2, 0≤z2≤0.4, 0.6≤(y2+z2)≤1, D is selected from one or more elements of Mn, Al, Zr, La, Ce, Ti, Mg, Nb, Ta, Mo and W; optionally, D includes Mn; The lithium-rich manganese-based positive electrode active material includes a lithium transition metal oxide with a chemical formula of pLi2MnO3·(1-p)LiZO2, where Z is selected from one or more elements of Ni, Co, Mn, Cr, Fe, Al, Nb, Mo and Ru.

14. The solid-state battery material according to any one of claims 1 to 13, wherein The particle size of the solid electrolyte body is 1 nm to 20 μm, and can be optionally 50 nm to 5 μm.

15. The solid-state battery material according to any one of claims 1 to 14, wherein The D of the coated electrolyte particles v 50 is 1nm~20μm, and can be selected as 50nm~5μm; D v 50 represents the particle size corresponding to when the cumulative volume distribution percentage of the multi-particle mixture reaches 50%.

16. The solid-state battery material according to any one of claims 1 to 15, wherein The sulfide electrolyte includes one or more of an argyrodite-type sulfide electrolyte, an LGPS-type sulfide electrolyte, and a lithium sulfide pentasulfide diphosphorus complex-type sulfide electrolyte.

17. The solid-state battery material according to claim 16, wherein: The sulfide electrolyte satisfies one or more of the following characteristics: The argyrodite-type electrolyte includes a chemical formula of Li 6±s P 1-j A j S 5±s-t B t X 1±s A sulfide electrolyte, wherein 0≤j<1, 0≤t<1, 0≤s<1, A is selected from one or more elements of Ge, Si, Sn and Sb, B is one or more elements of O, Se and Te, and X is selected from one or more elements of Cl, Br, I and F; The LGPS sulfide electrolyte includes a chemical formula of Li 10±δ5 Ge 1-g G g P 2-q Q q S 12-w W w A sulfide electrolyte, wherein 0≤δ5<1, 0≤g≤1, 0≤q≤2, 0≤w<1, G is selected from one or two elements of Si and Sn, Q is Sb, and W is selected from one or more elements of O, Se, Te, Cl, Br, I and F; The lithium sulfide - phosphorus pentasulfide composite sulfide electrolyte includes a sulfide electrolyte with the chemical formula (100 - u - v)Li2S·uP2S5·vM m N n , where 0 < u < 100, 0 ≤ v < 100, 0 ≤ u + v < 100, 0 ≤ m < 4, 0 ≤ n < 6, M is selected from one or more elements of Li, B, Ge, Si, Sn, and Sb, and N is selected from one or more elements of S, Se, Te, O, Cl, Br, I, and F.

18. The solid-state battery material according to any one of claims 1 to 17, wherein The solid-state battery material is a sulfide solid-state battery material.

19. The solid-state battery material according to any one of claims 1 to 18, wherein The solid-state battery material is a sulfide all-solid-state battery material.

20. A positive electrode active material layer comprising the solid-state battery material according to any one of claims 1 to 20.

21. The positive electrode active material layer according to claim 20, wherein The positive electrode active material layer includes positive electrode active particles; the positive electrode active particles include the coated positive electrode active particles, and the weight proportion of the coated positive electrode active particles in the positive electrode active material layer is 70wt% to 99wt%, and can be optionally 80wt% to 95wt%.

22. The positive electrode active material layer according to claim 20 or 21, wherein The positive electrode active material layer includes positive electrode electrolyte particles; the positive electrode electrolyte particles include the coated electrolyte particles, and the weight proportion of the coated electrolyte particles in the positive electrode active material layer is 0.1wt% to 30wt%, and can be optionally 5wt% to 20wt%.

23. A positive electrode film comprising a positive electrode active material layer, wherein the positive electrode active material layer comprises the solid-state battery material according to any one of claims 1 to 19, or the positive electrode active material layer is the positive electrode active material layer according to any one of claims 20 to 22. 24 . A solid electrolyte membrane comprising the solid-state battery material according to claim 1 , wherein the coated particles are the coated electrolyte particles.

25. A solid-state battery comprising a positive electrode layer, a solid electrolyte layer and a negative electrode layer; in, The solid-state battery meets one or more of the following characteristics: The positive electrode layer comprises a positive electrode active material layer according to any one of claims 20 to 22; The positive electrode layer comprises the positive electrode film according to claim 23; The solid electrolyte layer includes the solid electrolyte membrane according to claim 24 .

26. A solid-state battery comprising a positive electrode layer, a solid electrolyte layer and a negative electrode layer; The solid-state battery comprises one or more solid-state battery materials according to any one of claims 1 to 19; When the coated particles include the coated positive electrode active particles, the coated positive electrode active particles are located in the positive electrode layer; When the coated particles include the coated electrolyte particles, the coated electrolyte particles are located in at least one of the positive electrode layer and the solid electrolyte layer.

27. A solid-state battery comprising a positive electrode layer, a solid electrolyte layer, and a negative electrode layer; the positive electrode layer comprises a positive electrode active material layer, the positive electrode active material layer comprising positive electrode active particles and positive electrode electrolyte particles; At least one of the solid electrolyte layer and the positive electrode electrolyte particles comprises a sulfide electrolyte; The solid-state battery comprises one or more solid-state battery materials according to any one of claims 1 to 19; The solid-state battery satisfies at least one of the following characteristics: At least a portion of the positive electrode electrolyte particles contain a sulfide electrolyte, and the positive electrode active material layer includes at least one of the coated positive electrode active particles and the coated electrolyte particles; The solid electrolyte layer includes the coated electrolyte particles.

28. The solid-state battery according to claim 27, which satisfies one or more of the following characteristics: The solid electrolyte layer and the positive electrode electrolyte particles both contain a sulfide electrolyte, the sulfide electrolyte contained in the positive electrode electrolyte particles is recorded as a first sulfide electrolyte, and the sulfide electrolyte contained in the solid electrolyte layer is recorded as a second sulfide electrolyte, and the first sulfide electrolyte and the second sulfide electrolyte may be the same or different; The positive electrode electrolyte particles include a sulfide electrolyte, and at least one of the positive electrode active particles and the positive electrode electrolyte particles includes the coated particles.

29. The solid-state battery according to any one of claims 25 to 28, wherein The solid-state battery is a sulfide solid-state battery.

30. The solid-state battery according to any one of claims 25 to 29, wherein The solid-state battery is a sulfide all-solid-state battery.

31. An electrical device comprising the solid-state battery according to any one of claims 25 to 30.

32. Use of the solid-state battery material described in any one of claims 1 to 19, or the positive electrode active material layer described in any one of claims 20 to 22, or the positive electrode film described in claim 23, or the solid electrolyte membrane described in claim 24 in the preparation of a solid-state battery; optionally, the solid-state battery is a sulfide solid-state battery; further optionally, the solid-state battery is a sulfide all-solid-state battery.

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