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

Abstract

The present application relates to a solid-state battery material, a positive electrode active material layer, a positive electrode membrane, a solid electrolyte membrane, a solid-state battery, an electric device, and an application. The solid-state battery material comprises coated particles, wherein the coated particles comprise 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; wherein the coated particles comprise at least one of coated positive electrode active particles and coated electrolyte particles.

Description

Technology Field

[0001] Related applications

[0002] This application claims priority to a Chinese patent application filed on March 8, 2024, application number CN2024102711459, titled “Solid-state battery material, positive electrode active material layer, positive electrode membrane, solid electrolyte membrane, solid-state battery, electric device and application”, which is incorporated by reference in its entirety into this application.

[0003] The present application relates to the field of solid-state battery technology, and more specifically to solid-state battery materials, a positive electrode active material layer, a positive electrode film, a solid electrolyte film, a solid-state battery, an electric device, and applications. Background Technology

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

[0005] Solid-state batteries utilize non-flammable solid electrolytes to replace the organic electrolytes found in traditional liquid secondary batteries, significantly enhancing safety and are considered the next-generation batteries closest to industrialization. Comprehensively improving the discharge capacity and cycle performance of solid-state batteries is of significant importance in promoting their industrialization.

[0006] According to various embodiments and examples of the present application, the present application provides a solid battery material, a positive electrode active material layer, a positive electrode film, a solid electrolyte film, a solid battery, an electric device, and an application. An oxygen storage layer is installed in the solid battery material, and by using the solid battery material as a manufacturing raw material, the discharge capacity and cycle performance of a sulfide solid battery can be improved.

[0007] In a first aspect of the present application, a solid battery material comprising coated particles is provided, wherein the coated particles comprise 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;

[0008] Here, the coated particles comprise at least one of coated anode active particles and coated electrolyte particles;

[0009] When the above-mentioned coated particle is the above-mentioned coated anode-active particle, the particle body is an anode-active body, and the anode-active body includes an anode-active material;

[0010] When the above-mentioned coated particle is the above-mentioned coated electrolyte particle, the particle body is a solid electrolyte body, and the solid electrolyte body includes a sulfide electrolyte.

[0011] This solid battery material can be used as a sulfide solid battery material, and this solid battery material comprises coated particles having a surface oxygen storage layer installed thereon, wherein the oxygen storage layer is positioned on at least a portion of the surface of the coated particles; the coated particles may be positively active particles coated with a surface oxygen storage layer, may be sulfide-based electrolyte particles coated with a surface oxygen storage layer, or may be a combination of the two types of particles mentioned above coated with a surface oxygen storage layer. When manufacturing a sulfide solid battery using this solid battery material, the probability of contact between the sulfide electrolyte and oxygen can be reduced by utilizing the oxygen absorption effect of the oxygen storage material in the oxygen storage layer, thereby improving the chemical stability of the sulfide electrolyte during the battery manufacturing process, which is advantageous for fully exercising the role of rapid ion conduction of the sulfide electrolyte, thereby improving and promoting stable operation of the solid battery, and is advantageous for improving the discharge capacity and cycle performance of the sulfide solid battery.

[0012] The coated electrolyte particle comprises a solid electrolyte body and an oxygen storage layer located on at least a portion of the surface of the solid electrolyte body, the solid electrolyte body comprises a sulfide electrolyte, and the oxygen storage layer comprises an oxygen storage material. Accordingly, the coated electrolyte particle is a sulfide-based electrolyte particle with an oxygen storage layer installed on its surface, and the coated electrolyte particle can be used as a solid electrolyte in the solid electrolyte layer of a solid battery, and can also be used as a solid electrolyte in the electrode active material layer, and, for example, can be used as a solid electrolyte in the positive electrode active material layer. When coated electrolyte particles are used to manufacture individual solid electrolyte membranes or anode membranes, or to form an anode layer on a substrate (e.g., a solid electrolyte membrane), and during the process of manufacturing a solid-state battery using a membrane sheet containing these coated electrolyte particles, the oxygen storage layer installed on the surface of the coated electrolyte particles can serve to protect the sulfide electrolyte and reduce or prevent the decomposition of the sulfide electrolyte by oxygen in the air, thereby improving the chemical stability of the sulfide electrolyte during the battery manufacturing process. This is advantageous for the sulfide electrolyte to fully perform its role of rapid ion conduction, which promotes stable operation of the solid-state battery and is beneficial for improving the discharge capacity and cycle performance of the sulfide solid-state battery. Furthermore, the oxygen storage layer installed on the surface of the coated electrolyte particles can reduce or prevent direct contact between the sulfide electrolyte and moisture in the air, thereby suppressing the decomposition of the sulfide electrolyte and the generation of hydrogen sulfide gas, which is advantageous for improving the chemical stability of the sulfide electrolyte. Therefore, by installing an oxygen storage layer on the surface of the sulfide electrolyte, the oxygen storage material within the oxygen storage layer can absorb and store oxygen, and also block direct contact between the sulfide electrolyte and moisture, thereby providing superior air stability to the coated electrolyte particles.

[0013] The coated positive active particle comprises a positive active body and an oxygen storage layer located on at least a portion of the surface of the positive active body, wherein the positive active body comprises a positive active material and the oxygen storage layer comprises an oxygen storage material, and thus, the coated positive active particle is a positive active particle having an oxygen storage layer installed on its surface. This coated positive active particle can provide a positive active material to the positive layer of a solid-state battery. In the case of solid-state batteries, generally, anode electrolyte particles are installed on the anode active material layer of the anode layer to accelerate ion conduction, reduce interfacial impedance, and maximize the utilization of the anode active particle capacity. When the anode electrolyte particles are sulfide-based electrolytes, i.e., when they contain sulfide electrolytes, the oxygen storage layer installed on the surface of the coated anode active particles during the manufacturing process of the anode film, the anode layer of the solid-state battery, and the solid-state battery can absorb and store oxygen. This can reduce or prevent the erosion and decomposition of the sulfide electrolyte by oxygen in the air, thereby promoting stable operation of the solid-state battery. This is advantageous for fully utilizing the rapid ion conduction function of the sulfide electrolyte and reducing interfacial impedance, which promotes stable operation of the solid-state battery. Consequently, it is beneficial for improving the discharge capacity and cycle performance of the sulfide solid-state battery, and can also improve the scaling performance of the solid-state battery. Therefore, by installing an oxygen storage layer on the surface of the positive electrode active material, it can serve to protect 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, which is advantageous for improving the aforementioned electrochemical performance of the solid-state battery.

[0014] In some embodiments, the oxygen storage material comprises one or more of a lanthanide metal sulfate type oxygen storage material, a yttrium barium cobalt oxide type oxygen storage material, and a perovskite type oxygen storage material.

[0015] In some embodiments, the oxygen storage material is

[0016] The above lanthanide metal sulfate type oxygen storage material has the chemical formula Ln2O2SO4 - δ1 A phosphorus oxygen storage material comprising, wherein Ln is a lanthanide metal element, and the lanthanide metal element comprises one or more elements selected from La, Ce, Pr, Nd, Sm, Eu, Gd, and Tb, and 0≤δ1≤4;

[0017] The above yttrium barium cobalt oxide type oxygen storage material has the chemical formula (Y x M1 (1-x) )(Ba y M2 (1-y) )(Co z M3 (1-z) )4O 7+δ2 Includes a phosphorus oxygen storage material, wherein M1 is selected from one or more elements among Ca, In, Dy, Ho, Er, Tm, Yb, and Lu, M2 is Sr, M3 is selected from one or more elements among Mn, Fe, Ni, Cu, Zn, Al, Ga, and Zr, and 0≤x≤1, 0≤y≤1, 0≤z≤1, 0≤δ2≤1.5;

[0018] The above perovskite-type oxygen storage material has the chemical formula La1 - a A a Mn1 - b B b O3 - δ3 It includes an oxygen storage material, wherein A is selected from one or more elements among Sr, Y, Ce, Pr, and Nd, B is selected from one or more elements among Ni, Fe, Cu, and Co, and satisfies one or more of the characteristics such as 0≤a≤1, 0≤b≤1, and 0≤δ3≤1.

[0019] By selecting the aforementioned type of oxygen storage material, an oxygen storage layer can be formed on the surface of the positive active body or the solid electrolyte body. This allows for improved chemical stability of the sulfide electrolyte during the battery manufacturing process, which is advantageous for improving the discharge capacity and cycle performance of the sulfide solid battery.

[0020] In some embodiments, the weight ratio of the oxygen storage material in the coated particles is 0.1% to 10% by weight, and optionally 0.5% to 5% by weight.

[0021] In some embodiments, the thickness of the oxygen storage layer is 0.1 nm to 50 nm, and optionally 0.5 nm to 10 nm.

[0022] It can be understood that the amount of oxygen storage material coating can be controlled by controlling any of the parameters among the weight ratio of the coated particles of the oxygen storage material and the thickness of the oxygen storage layer, and that the amount of oxygen storage material coating can also be controlled by controlling these two parameters simultaneously. By controlling at least one of the parameters among the weight ratio of the coated particles of the oxygen storage material and the thickness of the oxygen storage layer within the aforementioned range, it is advantageous not only to improve the stability of the sulfide electrolyte component involved in the solid-state battery manufacturing process, but also to fully perform the role of rapid ion conduction of the sulfide electrolyte and to reduce interfacial resistance.

[0023] In some embodiments, the oxygen storage material comprises oxygen storage particles, and the particle size of the oxygen storage particles is 1 nm to 100 nm, optionally 1 nm to 50 nm.

[0024] The oxygen storage material located in the oxygen storage layer may be particulate oxygen storage particles, and in this case, the specific surface area of ​​the oxygen storage particles can be controlled by adjusting the particle size of the oxygen storage particles. When the particle size of the oxygen storage particles is controlled within the aforementioned range, it is advantageous to allow the oxygen storage particles to have a larger oxygen absorption surface, which is advantageous for the oxygen storage material to effectively perform its role of absorbing and storing oxygen, and also advantageous for it to perform its role of blocking moisture from the air.

[0025] In some embodiments, the particle size of the anode active body is 0.1 μm to 20 μm, and optionally 1 μm to 10 μm.

[0026] In some embodiments, D of the coated anodic active particles v 50 is 0.1 μm to 20 μm, optionally 1 μm to 10 μm; where, D v 50 represents the corresponding particle size when the cumulative volume distribution percentage of the multi-particle mixture reaches 50%.

[0027] D of coated positively active particles v The dimensional size of the coated anode active particles can be controlled by controlling at least one of the particle size of 50 and the anode active body. D of the coated anode active particles vBy controlling at least one parameter of the particle size of the anode active body within the range described above, it is advantageous to improve the discharge capacity of the coated anode active particles and maintain good contact between the coated anode active particles and the sulfide-based electrolyte in the composite anode. The active ion transport pathways inside the coated anode active particles having smaller dimensions are shorter, which is advantageous for improving the discharge capacity of the coated anode active particles themselves; the coated anode active particles having larger dimensions can be better coated by the sulfide-based electrolyte and have better interfacial contact with the sulfide-based electrolyte, which is advantageous for the cycle performance of the battery. Coated anode active particles with relatively moderate dimensions can enable the battery to achieve both high discharge capacity and excellent cycle performance.

[0028] In some embodiments, the anode active material comprises an oxide anode active material;

[0029] Optionally, the oxide cathode active material comprises a lithium transition metal oxide.

[0030] In some embodiments, the lithium transition metal oxide comprises one or more of a lithium cobalt oxide-type cathode active material, a high nickel cathode active material, a lithium-rich manganese-based cathode active material, and a modified form of any of the aforementioned cathode active materials, wherein the modified form comprises one or more of doping modification and coating modification;

[0031] Optionally,

[0032] The lithium cobalt oxide type cathode active material comprises a Li element, a Co element, and an O element, wherein the atomic molar ratio of the Co element and the O element is x2:2 and satisfies 0.9≤x2≤1; optionally, the lithium cobalt oxide type cathode active material comprises a Li element, a Co element, and an O element with an atomic molar ratio of 1:x2:2 and satisfies 0.9≤x2≤1;

[0033] The high-nickel anode active material comprises a Li element, a Ni element, and an O element, wherein the atomic molar ratio of the Ni element and the O element is y2:2 and satisfies 0.6≤y2≤1; optionally, the high-nickel anode active material comprises a Li element, a Ni element, and an O element with an atomic molar ratio of 1:y2:2 and satisfies 0.6≤y2≤1;

[0034] The above lithium-rich manganese-based cathode active material comprises Li, Mn, and O elements with an atomic molar ratio of (1+p):(p+r(1-p)):(2+p), and 0 <p≤1, 0≤r≤1을 충족한다.

[0035] In some embodiments, the lithium transition metal oxide is

[0036] 0.8≤y2≤1;

[0037] 0.2≤p≤1 satisfies one or more of the characteristics.

[0038] In some embodiments, the lithium transition metal oxide is

[0039] The above lithium cobalt oxide type cathode active material has the chemical formula LiCo x2 R1 - x2 It comprises a lithium transition metal oxide of O2, wherein R is selected from one or more elements among Ni, Mg, Ti, Al, Cr, Fe, Nb, and Ta;

[0040] The above-mentioned high-nickel cathode active material has the chemical formula LiNi y2 Co z2 D1 -y2- z2 It comprises a lithium transition metal oxide of O2, wherein 0≤z2≤0.4, 0.6≤(y2+z2)≤1, and D is selected from one or more elements among Mn, Al, Zr, La, Ce, Ti, Mg, Nb, Ta, Mo, and W; optionally, D comprises the element Mn;

[0041] The above lithium-rich manganese-based cathode active material comprises a lithium transition metal oxide having the chemical formula pLi2MnO3·(1-p)LiZO2, satisfying one or more of the characteristics such as Z being selected from one or more elements among Ni, Co, Mn, Cr, Fe, Al, Nb, Mo, and Ru.

[0042] When the anode active material among the anode active particles includes an oxide anode active material (e.g., lithium transition metal oxide), the oxide anode active material can release oxygen under high voltage operating conditions. By installing the aforementioned solid battery material on a positive electrode active material layer containing an oxide positive electrode active material (e.g., lithium transition metal oxide), direct contact between the oxide positive electrode active material and the sulfide electrolyte can be prevented, and oxygen released from the positive electrode can be absorbed through an oxygen storage material to suppress the attack of the released oxygen on the sulfide electrolyte, thereby further reducing the oxidative decomposition of the sulfide electrolyte by oxygen, suppressing interfacial side reactions between the oxide positive electrode active material (e.g., lithium transition metal oxide) and the sulfide electrolyte, and suppressing the increase in interfacial impedance. This is advantageous for improving the stability of the sulfide electrolyte within the positive electrode layer during the cycling process of the sulfide solid battery, thereby maintaining excellent conductivity, allowing the ionic conduction of the sulfide electrolyte to be exerted over the long term, and allowing the capacity of the positive electrode active particles to be fully exerted, thereby providing excellent high voltage stability to the sulfide solid battery. Additionally, the sulfide solid battery can be made to have higher initial Coulomb efficiency, higher discharge capacity, higher magnification performance, and better cycle performance. In addition, after a specific concentration of oxygen is stored in the oxygen storage material, the partial pressure of oxygen on the surface of the anode material increases, further hindering the release of oxygen from the anode material, which can enhance the structural stability of the anode material.

[0043] When the anode active material among the anode active particles includes an oxide anode active material (e.g., a lithium transition metal oxide), at least one parameter among the weight ratio of the coated particles of the oxygen storage material and the thickness of the oxygen storage layer can be controlled to simultaneously consider oxygen release suppression and good interfacial ion transport. This not only suppresses oxygen release and improves the stability of the sulfide electrolyte to achieve good discharge capacity and cycle performance, but also enables good interfacial ion transport to fully utilize the discharge capacity of the anode layer.

[0044] When the anode active material among the anode active particles includes an oxide anode active material (e.g., a lithium transition metal oxide), D of the coated anode active particles v By controlling at least one of the particle size of 50 and the anode active body, the amount of oxygen storage material in the oxygen storage layer relative to the anode active material contained within the anode active complement may also be indirectly controlled. D of the coated anode active particle v By controlling at least one parameter of the particle size of the anode active body within the range described above, the oxygen storage material is not only advantageous for providing sufficient oxygen absorption capacity, but also for improving the discharge capacity of the coated anode active particles and maintaining good contact between the coated anode active particles and the sulfide-based electrolyte in the composite anode.

[0045] Lithium transition metal oxides, such as lithium cobalt oxide-type cathode active materials, high-nickel cathode active materials, and lithium-rich manganese-based cathode active materials, readily release oxygen under high-voltage operating conditions. When using such lithium transition metal oxides as the cathode active material among cathode active particles, installing the aforementioned solid battery material in the cathode active material layer is advantageous for considering both high energy density and long cycle performance of sulfide solid batteries under conditions where oxygen release from the cathode is possible.

[0046] When a solid battery material installed in a positive electrode active material layer includes the aforementioned coated positive electrode active particles, additionally, it is advantageous for suppressing oxygen release from the positive electrode material, improving the crystal structural stability of the positive electrode active particles during battery cycling, and suppressing the formation of surface rock salt phases, thereby enabling sufficient positive electrode capacity and improving the long-cycle performance of the battery.

[0047] In some embodiments, the particle size of the solid electrolyte body is 1 nm to 20 μm, and optionally 50 nm to 5 μm.

[0048] In some embodiments, D of the coated electrolyte particles v 50 is 1 nm to 20 μm, optionally 50 nm to 5 μm; where, D v 50 represents the corresponding particle size when the cumulative volume distribution percentage of the multi-particle mixture reaches 50%.

[0049] D of coated electrolyte particles v The dimensional size of the coated electrolyte particles can be controlled by controlling at least one of the particle size of 50 and the solid electrolyte body. D of the coated electrolyte particles v By controlling at least one of the particle sizes of the solid electrolyte body and the coated electrolyte particles within the aforementioned range, it is advantageous to improve the overall ion conductivity of the membrane layer where the coated electrolyte particles are located, and to provide a superior electrical contact network, while also considering manufacturing costs and controlling the manufacturing cost of the solid electrolyte body and the amount of oxygen storage material required to manufacture the coated electrolyte particles. A relatively small particle size of the coated electrolyte particles is advantageous for improving electrical contact between positive active particles within the positive membrane or positive layer, thereby further promoting the capacity development of the solid-state battery. A relatively moderate particle size of the coated electrolyte particles is easier to manufacture.

[0050] In some embodiments, the sulfide electrolyte comprises one or more of an argyrodite-type sulfide electrolyte, an LGPS-type sulfide electrolyte, and a lithium sulfide-phosphorus pentasulfide complex-type sulfide electrolyte.

[0051] In some embodiments, the sulfide electrolyte is

[0052] The above argyrodite-type sulfide electrolyte has the chemical formula Li6 ± s P1 - j A j S5 ±s- t B t X1 ± s Comprising a phosphorus sulfide electrolyte, wherein 0≤j<1, 0≤t<1, 0≤s<1, A is selected from one or more elements among Ge, Si, Sn, and Sb, B is one or more elements among O, Se, and Te, and X is selected from one or more elements among Cl, Br, I, and F;

[0053] The above LGPS-type sulfide electrolyte has the chemical formula Li 10 ± δ5 Ge1 - g G g P2 - q Q q S 12 - w W w Comprising a phosphorus sulfide electrolyte, wherein 0≤δ5<1, 0≤g≤1, 0≤q≤2, 0≤w<1, G is selected from one or two elements among Si and Sn, Q is Sb, and W is selected from one or more elements among O, Se, Te, Cl, Br, I, and F;

[0054] The above lithium sulfide-phosphorus pentasulfide complex type sulfide electrolyte is (100-uv)Li2S·uP2S5·vM m N nContains a phosphorus sulfide electrolyte, where 0 <u<100, 0≤v<100, 0≤u+v<100, 0≤m<4, 0≤n<6이고, M은 Li, B, Ge, Si, Sn 및 Sb 중 하나 이상의 원소에서 선택되고, N은 S, Se, Te, O, Cl, Br, I 및 F 중 하나 이상의 원소에서 선택되는 것과 같은 특징 중 하나 이상을 충족한다.

[0055] By using the aforementioned solid-state battery material, sulfide electrolytes having a high ion transport rate can be used more flexibly in sulfide solid-state batteries, thereby significantly reducing the limitations on material selection for sulfide electrolytes.

[0056] In some embodiments, the solid battery material is a sulfide solid battery material.

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

[0058] In a second aspect of the present application, a positive active material layer comprising a solid battery material according to the first aspect of the present application is provided.

[0059] The positive active material layer provided in the second aspect of the present application comprises at least one of coated positive active particles and coated electrolyte particles. When this positive active material layer is applied to a sulfide solid-state battery, the probability of contact between the sulfide electrolyte and oxygen can be reduced by utilizing the oxygen absorption effect of the oxygen storage material in the oxygen storage layer. This improves the chemical stability of the sulfide electrolyte during the battery manufacturing process, which is advantageous for fully utilizing the rapid ion conduction function of the sulfide electrolyte, thereby promoting stable operation of the solid-state battery and improving the discharge capacity and cycle performance of the sulfide solid-state battery. Additionally, the oxygen storage layer installed on the surface of the coated electrolyte particles can reduce or separate direct contact between the sulfide electrolyte and moisture in the air, which can suppress the decomposition of the sulfide electrolyte and the generation of hydrogen sulfide gas, thereby improving the chemical stability of the sulfide electrolyte.

[0060] In some embodiments, the anode active material layer comprises anode active particles; the anode active particles comprise coated anode active particles, and the weight ratio of the coated anode active particles in the anode active material layer is 70% to 99% by weight, and optionally 80% to 95% by weight.

[0061] In some embodiments, the anode active material layer comprises anode electrolyte particles; the anode electrolyte particles comprise coated electrolyte particles, and the weight ratio of the coated electrolyte particles in the anode active material layer is 0.1% to 30% by weight, and optionally 5% to 20% by weight.

[0062] By controlling the weight ratio of coated anode active particles in the anode active material layer within the aforementioned range, it is advantageous to consider both high energy density and cycle stability.

[0063] When a sulfide-based electrolyte is included in the anode active material layer, controlling the weight ratio of the coated anode active particles in the anode active material layer within the aforementioned range is also advantageous for achieving a combination and balance between high energy density and reduced oxidative decomposition of the sulfide electrolyte contained in the sulfide-based electrolyte.

[0064] The weight percentage of coated electrolyte particles in the anode active material layer can be controlled within the aforementioned range, which is advantageous for enabling the anode film to provide superior overall ion conductivity.

[0065] In a third aspect of the present application, an anode film comprising an anode active material layer is provided, wherein the anode active material layer comprises a solid battery material according to the first aspect of the present application, or the anode active material layer is an anode active material layer according to the second aspect of the present application.

[0066] This anode film includes an anode active material layer according to the second aspect of the present application.

[0067] In a fourth aspect of the present application, a solid electrolyte membrane comprising a solid battery material according to the first aspect of the present application is provided, wherein the coated particles are the coated electrolyte particles.

[0068] This solid electrolyte membrane comprises coated electrolyte particles, and an oxygen storage layer installed on the surface of the coated electrolyte particles can reduce or isolate the decomposition of the sulfide electrolyte by oxygen in the air, and can also reduce or separate direct contact between the sulfide electrolyte and moisture in the air, thereby suppressing the decomposition of the sulfide electrolyte and the generation of hydrogen sulfide gas. This can improve the chemical stability of the sulfide electrolyte and the stability of the ion conductivity of the solid electrolyte membrane during the battery manufacturing process, promote stable operation of the solid battery, and is advantageous for improving the discharge capacity and cycle performance of the sulfide solid battery.

[0069] In the fifth aspect of the present application, a solid-state battery comprising a solid-state battery material according to the first aspect of the present application is provided.

[0070] In some embodiments, a solid-state battery comprising an anode layer, a solid electrolyte layer, and a cathode layer is provided;

[0071] Here, the solid-state battery is

[0072] The above anode layer comprises an anode active material layer according to the second aspect of the present application;

[0073] The above anode layer comprises an anode film according to the third aspect of the present application;

[0074] The above-mentioned solid electrolyte layer satisfies one or more of the features such as including a solid electrolyte membrane according to the fourth aspect of the present application.

[0075] In some embodiments, a solid-state battery comprising an anode layer, a solid electrolyte layer, and a cathode layer is provided;

[0076] The above-mentioned solid-state battery comprises one or more solid-state battery materials according to the first aspect of the present application;

[0077] When the above-mentioned coated particles include the above-mentioned coated anode active particles, the above-mentioned coated anode active particles are located in the anode layer;

[0078] When the above-mentioned coated particles include the above-mentioned coated electrolyte particles, the above-mentioned coated electrolyte particles are located in at least one of the anode layer and the above-mentioned solid electrolyte layer.

[0079] In some embodiments, a solid-state battery is provided comprising an anode layer, a solid electrolyte layer, and a cathode layer; wherein the anode layer comprises an anode active material layer, and the anode active material layer comprises anode active particles and anode electrolyte particles;

[0080] At least one of the above solid electrolyte layer and the above anode electrolyte particles comprises a sulfide electrolyte;

[0081] The above-mentioned solid-state battery comprises one or more solid-state battery materials according to the first aspect of the present application;

[0082] The above solid-state battery

[0083] At least some of the above-mentioned anode electrolyte particles comprise a sulfide electrolyte, and the anode active material layer comprises at least one of the coated anode active particles and the coated electrolyte particles;

[0084] The above solid electrolyte layer satisfies at least one of the characteristics, such as including the coated electrolyte particles.

[0085] In some embodiments, the solid-state battery

[0086] The above solid electrolyte layer and the above anode electrolyte particles both contain a sulfide electrolyte, the sulfide electrolyte contained in the above anode electrolyte particles is designated as a first sulfide electrolyte, the sulfide electrolyte contained in the above solid electrolyte layer is designated as a second sulfide electrolyte, and the first sulfide electrolyte and the second sulfide electrolyte may be the same or different;

[0087] The above-mentioned anode electrolyte particles satisfy one or more of the following characteristics, such as comprising a sulfide electrolyte, and at least one of the anode active particles and the anode electrolyte particles comprising the coated particles.

[0088] As described above, in the case of a solid-state battery (sulfide solid-state battery) in which the aforementioned solid-state battery material is installed in at least one of the anode layer and the solid electrolyte layer, when at least one of the anode active particles or coated electrolyte particles is used in the anode layer, when electrolyte particles are used in the solid electrolyte layer, or when the aforementioned solid-state battery material is used in both the anode layer and the solid electrolyte layer, it is advantageous to improve the discharge capacity and cycle performance of the solid-state battery.

[0089] In some embodiments, the solid-state battery is a sulfide solid-state battery.

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

[0091] In the sixth aspect of the present application, an electric device comprising a solid-state battery according to the fourth aspect of the present application is provided.

[0092] In a seventh aspect of the present application, the application of a solid battery material according to the first aspect of the present application, or a positive electrode active material layer according to the second aspect of the present application, or a positive electrode film according to the third aspect of the present application, or a solid electrolyte film according to the fourth aspect of the present application is provided in the manufacture of a solid battery; optionally, the solid battery is a sulfide solid battery; more optionally, the solid battery is a sulfide all-solid battery.

[0093] Details regarding one or more embodiments or examples of the present application are set forth in the drawings and description below. Other features, purposes, and advantages of the present application will become apparent from the specification, drawings, and claims. Brief explanation of the drawing

[0094] To better describe and explain the embodiments, examples, or illustrations provided in this application, one or more drawings may be referenced. Additional details or illustrations for describing the drawings should not be construed as limiting the scope of any of the disclosed application, the embodiments, examples, or illustrations currently described, or the best mode currently understood for such application. It should also be explained that the drawings are all drawn in a simplified form and are intended only to assist in the convenient and clear description of this application. The various dimensions of each component shown in the drawings are arbitrary and may be accurate and may not be drawn according to actual proportions. For example, to illustrate the drawings more clearly, the dimensions of components in some parts of the drawings have been appropriately exaggerated. Unless otherwise stated, each component in the drawings is not drawn according to actual proportions. Each drawing of this application does not limit each dimension of each component. Also, the same component is indicated by the same reference numeral throughout the drawings. In the drawings: FIG. 1 is a schematic diagram of the structure of a coated particle in a solid battery material provided in one embodiment of the present application, and the coated particle includes a particle body and an oxygen storage layer located on the surface of the particle body. FIG. 2 is a schematic diagram of the structure of a coated particle in a solid battery material provided in one embodiment of the present application, wherein the coated particle comprises a particle body and an oxygen storage layer located on the surface of the particle body, and the oxygen storage layer comprises an oxygen storage material. FIG. 3 is a schematic diagram of the structure of two types of coated particles related to some embodiments of the present application, one being a coated anode active particle and the other being a coated electrolyte particle; the coated anode active particle comprises an anode active body and an oxygen storage layer located on the surface of the anode active body, and the oxygen storage layer comprises an oxygen storage material; the coated electrolyte particle comprises a solid electrolyte body and an oxygen storage layer located on the surface of the solid electrolyte body, and the oxygen storage layer comprises an oxygen storage material. FIG. 4 is a schematic diagram of the structure of an anode active material layer in some embodiments of the present application, and the anode active material layer includes coated electrolyte particles. FIG. 5 is a schematic diagram of the structure of an anode active material layer in some embodiments of the present application, and the anode active material layer comprises coated anode active particles. FIG. 6 is a schematic diagram of the structure of an anode active material layer in some embodiments of the present application, and the anode active material layer comprises coated electrolyte particles and coated anode active particles. FIG. 7 is a schematic diagram of the structure of a positive active material layer in some embodiments of the present application, and the positive active material layer comprises coated positive active particles and a sulfide-based electrolyte without an oxygen storage layer. FIG. 8 is a schematic diagram of the structure of a positive active material layer in some embodiments of the present application, and the positive active material layer comprises a coated electrolyte particle and a positive active particle without an oxygen storage layer. FIG. 9 is a schematic diagram of the structure of a solid electrolyte membrane in some embodiments of the present application, and the solid electrolyte membrane is a solid electrolyte membrane comprising coated electrolyte particles. FIG. 10 is a schematic diagram of the structure of a solid electrolyte membrane used in a solid battery provided in some embodiments of the present application, and the solid electrolyte membrane is a solid electrolyte membrane comprising a sulfide-based electrolyte without an oxygen storage layer. FIG. 11 is a schematic diagram of the structure of a solid electrolyte layer in a solid battery provided in some embodiments of the present application, and the solid electrolyte layer is a solid electrolyte layer comprising coated electrolyte particles. FIG. 12 is a schematic diagram of the structure of a solid electrolyte layer in a solid battery provided in some embodiments of the present application, and the solid electrolyte layer is a solid electrolyte layer comprising a sulfide-based electrolyte without an oxygen storage layer. FIG. 13 is a schematic diagram of the structure of an anode film according to one embodiment of the present application, and the anode film includes an anode current collector and an anode active material layer located on one side of the anode current collector. FIG. 14 is a schematic diagram of the structure of an anode film according to one embodiment of the present application, and the anode film includes an anode current collector and a positive active material layer located on both sides of the anode current collector. FIG. 15 is a schematic diagram of the structure of a solid cell according to one embodiment of the present application, and the solid cell includes a positive electrode layer, a solid electrolyte layer, and a negative electrode layer stacked sequentially. FIG. 16 is a schematic diagram of the structure of an embodiment of a solid cell illustrated in FIG. 15, wherein the solid cell comprises a positive electrode layer, a solid electrolyte layer, and a negative electrode layer stacked sequentially, wherein the positive electrode layer comprises a positive film according to an embodiment of the present application, and the positive film comprises a positive current collector and a positive active material layer located on both sides of the positive current collector, and the positive active material layer is installed between the positive current collector and the solid electrolyte layer. FIG. 17 is a schematic diagram of a solid-state battery cell according to one embodiment of the present application. FIG. 18 is an exploded view of a solid-state battery cell according to one embodiment of the present application shown in FIG. 17. FIG. 19 is a schematic diagram of a battery module according to one embodiment of the present application. FIG. 20 is a schematic diagram of a battery pack according to one embodiment of the present application. FIG. 21 is an exploded view of a battery pack according to one embodiment of the present application shown in FIG. 20. FIG. 22 is a schematic diagram of an electric device using a solid-state battery as a power source according to one embodiment of the present application. FIG. 23 is an X-ray diffraction (XRD) pattern of a YBaCo4O7 oxygen storage material used in one embodiment of the present application, and the horizontal axis “angle” corresponds to 2θ(°). FIG. 24 is a transmission electron microscope (TEM) image of a coated anode-active particle provided in some embodiment of the present application, and the anode-active body is NCM 811 And, the thickness of the oxygen storage layer shown in the drawing is about 2 nm. Specific details for implementing the invention

[0095] Hereinafter, with appropriate reference to the drawings, some embodiments of the solid-state battery material, positive active material layer, positive film, solid electrolyte film, solid-state battery, electric device, and application of the present application are described in detail. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of known matters and redundant descriptions of identical structures may be omitted. This is to avoid making the following description unnecessarily verbose and to aid the understanding of those skilled in the art. Furthermore, the drawings and the following description are provided to enable those skilled in the art to fully understand the present application and are not intended to limit the subject matter described in the claims.

[0096] The “range” disclosed in this application may be limited in the form of lower and upper limits, and a given range is limited by selecting one lower limit and one upper limit, and the selected lower limit and upper limit define the boundaries of a specific range. A range limited in this way may include or not include end values, any end values ​​may be included or not included independently, and may be combined arbitrarily, that is, any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60 to 120 and 80 to 110 are listed for a specific parameter, it is expected that they are understood as ranges of 60 to 110 and 80 to 120. Furthermore, if minimum range values ​​1 and 2 are listed and maximum range values ​​3, 4 and 5 are also listed, the ranges described below may all be expected to be 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4, and 2 to 5. In this application, unless otherwise stated, the numerical range “a to b” is represented as an abbreviation for any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range “0 to 5” indicates that all real numbers between “0 to 5” are already listed in this application, and “0 to 5” is merely an abbreviation for such combination of numbers. Furthermore, if one parameter is an integer ≥ 2, this parameter is listed as, for example, integers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc. For example, if a specific parameter is an integer selected from “2 to 10,” it is listed as integers 2, 3, 4, 5, 6, 7, 8, 9, 10.

[0097] In this application, unless otherwise specified, “about” indicates a reasonable range based on the figures, and the range of variation may vary depending on the type and value of the figures. For example, a range of ±10%, ±5%, ±2%, ±1%, etc. may be allowed. For example, if the approximation is ±1°C for “about 20°C”, then approximations such as 19°C, 19.5°C, etc., which are within the approximation range indicated as “about 20°C”, must also be included in the range indicated as “about 20°C”.

[0098] In this application, for example, “plural,” “multiple,” “many,” “several,” etc. refer to two or more numbers unless otherwise specified. For example, “one or more” indicates one or two or more types. Where in relation to the item “any plural,” it may be understood to refer to any appropriate combination of plural items, that is, a combination of “any plural” items in a manner that enables the implementation of this application without conflict.

[0099] Unless otherwise specified, all embodiments and optional embodiments of the present application may be combined with one another to form a new technical solution.

[0100] The term "Examples" as used in this application refers to the combination of specific features, structures, or characteristics described in the Examples, which may be included in at least one Example or Embodiment of this application. The appearance of such phrases at each location within the specification does not imply that they all refer to the same Example, nor are they independent or alternative Examples excluded from each other. It is an explicit and implicit understanding by those skilled in the art that the Examples described in this application may be combined with other Examples. The term "Embodiments" as used herein has a similar understanding.

[0101] A person skilled in the art will understand that in the method of each embodiment or example, the order of each step does not imply a strict order of execution and does not constitute any limitation on the course of execution, and the detailed order of execution of each step is determined according to function and possible internal logic. Unless otherwise specified, all steps of the present application may be performed sequentially, may be performed randomly, and preferably may be performed sequentially. For example, the method may include steps (a) and (b), which indicates that the method may include steps (a) and (b) performed sequentially and steps (b) and (a) performed sequentially. For example, the method M may further include step (c), which indicates that step (c) may be added to the method in any order, and for example, the method M may include steps (a), (b), and (c), may include steps (a), (c), and (b), and may include steps (c), (a), and (b).

[0102] In the present application, regarding open technical features or technical solutions described by words such as "containing," "comprehensive," or "include," additional members other than those enumerated are not excluded unless otherwise specified, and it may be deemed to provide not only closed features or solutions composed of enumerated members, but also open features or solutions including additional members other than those enumerated. For example, A includes a1, a2, and a3, and unless otherwise specified, may include other members or not include additional members, and may be deemed to provide features or solutions such as "A consists of a1, a2, and a3" or "A is selected from a1, a2, and a3," but also features or solutions such as "A includes other members in addition to a1, a2, and a3."

[0103] In this application, unless otherwise specified, A (e.g., B) indicates that B is a non-limiting example of A and it can be understood that A is not limited to B.

[0104] In this application, "optional," "optional," and "optional" indicate that options may or may not be available, that is, selected from one of two parallel solution means of "present" or "absent." If there are multiple "optional" items in the technical solution means, each "optional" item is independent unless otherwise specified and there is no contradiction or mutual constraint. Unless otherwise specified, descriptions such as "optionally included" and "optionally contained" in this application indicate "may include or not include," using "optionally included" as an example.

[0105] In this application, unless otherwise specified, a feature or solution corresponding to “and / or” comprises any of two or more listed related items, and any and all combinations of listed related items, wherein any and all combinations comprise two of the listed related items, any more of the listed related items, or a combination of all listed related items. For example, “A and / or B” represents a group consisting of A, B, and “a combination of A and B.” Here, “comprising A and / or B” may mean “comprising A, comprising B, and comprising both A and B,” and may mean “comprising A, comprising B, or comprising both A and B,” and may be appropriately understood according to the context.

[0106] The terms used herein, such as “combination of these,” “any combination of these,” and “any combination of these,” include all appropriate combination methods of any two or more of the listed items.

[0107] In this application, the term "appropriate" in phrases such as "appropriate combination method," "appropriate method," and "any appropriate method" is based on the ability to implement the technical solution of the present application.

[0108] It should be understood that, herein, "preferably," "better," "more desirable," "suitable," "better," and "better desirable" refer merely to embodiments or examples with superior effects and do not limit the scope of protection of this application. If there are multiple "preferably" items in the technical solution, each "preferably" item is independent unless otherwise specified and there is no contradiction or mutual constraint.

[0109] In this application, terms such as “more,” “further,” “particularly,” “for example,” “for instance,” “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.

[0110] In this application, terms such as “First Aspect,” “Second Aspect,” “Third Aspect,” “Fourth Aspect,” “Fifth Aspect,” “Sixth Aspect,” “Seventh Aspect,” etc., including “First Aspect,” “Second Aspect,” “Third Aspect,” “Fourth Aspect,” “Fifth Aspect,” “Sixth Aspect,” “Seventh Aspect,” etc., are used solely for descriptive purposes and should not be understood as indicating or implying relative importance or number, nor should they be understood as implicitly indicating the importance or number of the described technical features. Furthermore, “First,” “Second,” “Third,” “Fourth,” “Fifth,” “Sixth Aspect,” “Seventh Aspect,” etc., are used solely for non-strict enumeration and descriptive purposes and should be understood as not constituting a restrictive limitation on the number.

[0111] In this application, unless otherwise specified or limited, the first feature being "above" or "below" the second feature may mean that the first feature and the second feature are in direct contact or that the first feature and the second feature are indirectly contacted through an intermediate medium. In this application, unless otherwise specified or limited, the first feature being "above" or "below" the second feature may indicate a mutual positional relationship in horizontal height, or it may indicate only the existence of an attachment relationship without limiting the mutual positional relationship in horizontal height.

[0112] 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.

[0113] In this application, when referring to units of a data range, if the unit is present only after the right end point, it indicates that the units of the left end point and the right end point are the same. For example, 3 to 5h or 3-5h indicates that the units of the left end point "3" and the right end point "5" are both h (hours), and both have the same meaning as 3h to 5h. Furthermore, similar descriptions of other parameters, such as temperature and dimensions, are understood in the same manner.

[0114] The weight or mass of the relevant components mentioned in the embodiments or examples of this application may not only represent the content of each component but also the proportional relationship of weight or mass between each component; thus, as long as the content of the relevant components according to the embodiments or examples of this application is proportionally expanded or reduced according to the ratio, this falls within the scope disclosed in this application. Additionally, the masses related to the embodiments or examples of this application may be mass units known in the chemical industry, such as micrograms (μg), milligrams (mg), grams (g), or kilograms (kg). Unless otherwise specified, mass ratios are equal to corresponding weight ratios; for example, if the mass of substance A is m1 and its weight is W1, and the mass of substance B is m2 and its weight is W2, the mass ratio m1 / m2 of the two is numerically equal to the corresponding weight ratio W1 / W2.

[0115] In this application, unless otherwise specified, weight% represents a weight percentage based on weight and is numerically equivalent to a corresponding mass percentage based on mass. In this application, when weight percentage is denoted as "0", it has the same meaning as "0 weight%" and may be used interchangeably.

[0116] For the parameter units related in this application, unless otherwise specified, nm represents nanometers, μm represents micrometers, S / cm represents Siemens / centimeter, V represents volts, mPa·S represents millipascals / second, and mg / cm² 2 represents milligrams per square centimeter, and g / cm 2 represents grams per square centimeter, and g / cm 3 represents grams / cubic centimeter, °C represents degrees Celsius, mA / g represents milliampere / gram, and mAh / g represents milliampere-hour / gram.

[0117] In this application, "greater than or equal to," "greater than or equal to," and "≥" have the same meaning and may be used interchangeably; "less than or equal to," "less than or equal to," and "≤" also have the same meaning and may be used interchangeably; "greater than" may be equivalently represented as ">" and "less than" may be equivalently represented as "<". In this application, unless otherwise specified, "greater than or equal to" and "≥" may be deemed to provide two types of solutions, namely "greater than" and "equal to". In this application, unless otherwise specified, "less than or equal to" and "≤" may be deemed to provide two types of solutions, namely "less than" and "equal to".

[0118] In this application, related exemplary descriptions such as “in some embodiments (or examples)” and “in one embodiment (or example)” may include, but are not limited to: such means of solution may be combined with other means of solution in an appropriate manner to form new technical means of solution.

[0119] In this application, unless otherwise specified, the term "solid battery" provided herein refers to a battery in which the electrolyte within the battery comprises a solid electrolyte; generally, a solid battery comprises a positive electrode layer, a solid electrolyte layer, and a negative electrode layer. During the charging and discharging process of the battery, active ions are reciprocally inserted into and removed between the positive electrode layer and the negative electrode layer. Since the solid electrolyte layer acts as an ion conductor between the positive electrode layer and the negative electrode layer and can also serve to separate the positive electrode layer and the negative electrode layer to prevent short circuits between them, a separator, as found in conventional lithium-ion batteries, may not be installed in a solid battery. Solid batteries have significantly improved battery safety by using a non-flammable solid electrolyte to replace the organic electrolyte of traditional liquid lithium batteries. In addition to improving safety, solid batteries can better adapt to high-energy-density positive and negative electrode materials and reduce system weight, making them advantageous for consideration in conjunction with energy density improvement.

[0120] In this application, unless otherwise specified, "solid battery" in any embodiment or example may be a sulfide solid battery. Unless otherwise specified, "sulfide solid battery" refers to a solid battery in which the electrolyte associated with the battery comprises a sulfide-based solid electrolyte. For example, the sulfide-based solid electrolyte may be located in the positive electrode layer of the sulfide solid battery and may also be located in the solid electrolyte layer. The sulfide solid battery may additionally be an all-solid battery.

[0121] In this application, unless otherwise specified, "all-solid-state battery" refers to a solid-state battery in which the electrolyte in the battery is entirely a solid electrolyte. In this case, the positive electrode layer, the negative electrode layer, and the electrolyte portion all use solid materials, and since no liquid electrolyte is installed in the battery, it may be referred to as an "all-solid-state battery."

[0122] In this application, unless otherwise specified, the "solid battery" in any embodiment or example may be, but is not limited to, a sulfide all-solid-state battery. Unless otherwise specified, the "sulfide all-solid-state battery" refers to an all-solid-state battery in which the electrolyte associated with the battery comprises a sulfide-based solid electrolyte. Here, the sulfide-based solid electrolyte may be located in the positive electrode layer of the sulfide all-solid-state battery and may also be located in the solid electrolyte layer.

[0123] In this application, unless otherwise specified, "solid electrolyte" refers to an electrolyte material or electrolyte substance that exists in a solid form during the storage and manufacturing processes of the solid battery and the components constituting the solid battery, as well as during the operation of the solid battery. It may be understood that the solid electrolyte includes, but is not limited to, existing in a solid form at room temperature.

[0124] In this application, unless otherwise specified, the electrode layer may be an anode layer or a cathode layer, and the "active material" in the electrode layer refers to a material having the ability to reversibly insert and escape active ions. Unless otherwise specified, the "cathode active material" refers to a material used in the cathode layer having the ability to reversibly insert and escape active ions, and the "anode active material" refers to a material used in the anode layer having the ability to reversibly insert and escape active ions. When charging the solid-state battery, active ions escape from the anode and are inserted into the cathode through the solid electrolyte layer; when discharging the solid-state battery, active ions escape from the cathode and are inserted into the anode. There are no specific limitations on the active ions, and without limitation, the active ions may be lithium ions, corresponding to a lithium-ion solid-state battery.

[0125] In this application, "electrode active material," "electrode active substance," "active material," and "active substance" have the same meaning and may be used interchangeably; "anode active substance" and "anode active material" have the same meaning and may be used interchangeably; and "cathode active substance" and "cathode active material" have the same meaning and may be used interchangeably.

[0126] In this application, unless otherwise specified, the "electrode active material layer" comprises at least one of the positive active material layer in the positive layer and the negative active material layer in the negative layer, and depending on the specific circumstances, the electrode active material layer may refer to the positive active material layer or the negative active material layer. It may be understood that the positive active material layer contains a positive active material, and the negative active material layer contains a negative active material. In this application, the "electrode active material layer" may also be briefly referred to as the "active material layer."

[0127] In the present application, unless otherwise specified, the anode layer comprises at least an anode active material layer.

[0128] In this application, unless otherwise specified, the anode active material layer comprises at least anode active particles and generally further comprises anode electrolyte particles.

[0129] In this application, unless otherwise specified, "anode-active particle" refers to a particle containing an anode-active material having the ability to reversibly escape and insert active ions.

[0130] In this application, unless otherwise specified, "anode electrolyte particles" and "anode solid electrolyte" have the same meaning and can be used interchangeably, referring to a solid electrolyte that can be used in an anode membrane or anode layer. The anode electrolyte particles can enhance the ion conductivity of the anode membrane or anode layer and reduce interfacial impedance, thereby promoting sufficient release of charge transfer efficiency and capacity between the anode active material and the outside.

[0131] In this application, unless otherwise specified, "negatively active particles" refers to particles containing a negatively active material having the ability to reversibly insert and escape active ions.

[0132] Except for using solid electrolyte materials in the solid electrolyte layer, solid electrolyte materials are generally installed in the anode layer as well. Currently, the common approach for solid-state batteries is to use a composite anode system on the anode side, installing both the anode active material and the solid electrolyte simultaneously at the anode. This method utilizes the solid electrolyte to enhance the ionic conductivity of the anode side, promotes the sufficient release of charge transfer efficiency and capacity between the anode active material and the external environment to reduce impedance, and simultaneously improves the cycle stability of the battery by transferring electrons using the electron conductivity of the anode active material itself. Among various solid electrolyte materials, sulfide solid electrolytes exhibit very high ionic conductivity (approximately 10 -3 ~10 -2 Due to its superior flexibility and S / cm (nearly equivalent to commercial liquid electrolytes), it possesses excellent ion conductivity and good deformation capability, making it the most promising solid electrolyte material for practical application and industrialization.

[0133] However, the air stability of sulfide solid electrolytes is poor and they are sensitive to moisture and oxygen in the air. They readily release air and hydrogen sulfide gas, which degrades ionic conductivity and poses certain safety risks, severely limiting the practical application of sulfide solid electrolytes.

[0134] On the other hand, sulfide solid electrolytes easily absorb moisture from the air and react to produce toxic hydrogen sulfide gas, which also impairs the rapid ion conductivity of the sulfide solid electrolyte. During the manufacturing process of solid-state batteries, the anode layer and the solid electrolyte layer inevitably come into contact with moisture from the air. Due to the instability of the sulfide electrolyte in air during the manufacturing and assembly process of the solid-state battery, the sulfide solid electrolyte in the anode layer and the solid electrolyte layer decomposes, impairing ion conductivity. This increases the interfacial impedance between the anode active particles and the anode electrolyte particles within the anode layer, and between the anode layer and the solid electrolyte layer, thereby affecting the electrochemical performance of the manufactured solid-state battery and damaging the battery's cycle performance.

[0135] On the other hand, sulfide solid electrolytes have the disadvantage of being susceptible to oxidation and decomposition. Furthermore, oxygen in the air and oxygen released from the anode layer during battery operation can attack the sulfide solid electrolyte, causing it to oxidize and decompose. This reduces the rapid ion conductivity of the sulfide solid electrolyte, increases the internal impedance of the anode layer and the interfacial impedance between the anode layer and the solid electrolyte layer, degrades the electrochemical performance of the manufactured solid-state battery, and impairs the battery's cycle performance.

[0136] Based on this, according to various embodiments and various examples of the present application, the embodiments and various examples of the present application provide at least a solid battery material, a positive electrode active material layer, a positive electrode film, a solid electrolyte film, a solid battery, an electric device, and an application. By using this solid battery material as a manufacturing raw material, the discharge capacity and cycle performance of a sulfide solid battery can be improved.

[0137] In a first aspect of the present application, a solid-state battery material comprising coated particles is provided, wherein the coated particles comprise 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;

[0138] Here, the coated particles comprise at least one of coated anode-active particles and coated electrolyte particles;

[0139] In the case where the coated particle is a coated anode-active particle, the particle body is an anode-active body, and the anode-active body includes an anode-active material;

[0140] In the case where the coated particle is a coated electrolyte particle, the particle body is a solid electrolyte body, and the solid electrolyte body contains a sulfide electrolyte.

[0141] In this application, unless otherwise specified, "solid battery material" refers to a material that can be applied to a solid battery, but is not limited to such application. Unless otherwise specified, no liquid electrolyte is present in the material, excluding particles coated on the solid battery material.

[0142] In some embodiments, the solid battery material may be a sulfide solid battery material. Unless otherwise specified, "sulfide solid battery material" is a material that can be applied to a sulfide solid battery, but is not limited to such application. Unless otherwise specified, the sulfide solid battery material comprises a sulfide-based solid electrolyte. For example, if the sulfide solid battery material comprises coated electrolyte particles, the coated electrolyte particles themselves are a sulfide-based solid electrolyte; and also, for example, if the sulfide solid battery material comprises coated positive active particles, the sulfide solid battery material also comprises a sulfide-based electrolyte.

[0143] For example, sulfide solid battery materials may additionally be all-solid-state battery materials. Unless otherwise specified, "all-solid-state battery materials" are materials that can be applied to all-solid-state batteries, but are not limited to such applications. Unless otherwise specified, all-solid-state battery materials do not contain liquid electrolytes.

[0144] In some embodiments, the solid battery material may be a sulfide all-solid-state battery material. Unless otherwise specified, "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 such application. Unless otherwise specified, the sulfide all-solid-state battery material comprises a sulfide-based solid electrolyte and does not include a liquid electrolyte. For example, if the sulfide all-solid-state battery material comprises coated electrolyte particles, the coated electrolyte particles are a sulfide-based solid electrolyte; and also, for example, if the sulfide all-solid-state battery material comprises coated positive electrode active particles, the sulfide all-solid-state battery material also comprises a sulfide-based electrolyte.

[0145] In this application, unless otherwise specified, the "solid battery" related to the embodiments or examples of this application may be a sulfide solid battery.

[0146] In some embodiments, the "sulfide solid battery" comprises a sulfide-based electrolyte in at least one of the solid electrolyte layer and the positive electrode active material layer.

[0147] In this application, unless otherwise specified, "sulfide electrolyte," "sulfide electrolyte component," and "sulfide solid electrolyte component" have the same meaning and may be used interchangeably; they refer to a solid electrolyte component in the form of a sulfide, and the sulfide electrolyte includes the presence of a sulfur (S) element in the form of a sulfide. The "sulfide electrolyte" related to the embodiments or examples of this application is not particularly limited in its form of existence and may be an independent sulfide electrolyte material, may be a part of a composite material, or, for example, may be a sulfide electrolyte component located inside a coated electrolyte particle (wherein the solid electrolyte body of the coated electrolyte particle includes the sulfide electrolyte). The "sulfide electrolyte" related to the embodiments or examples of this application may be located within either a solid electrolyte layer or an anode layer, may be included in an anode electrolyte particle, or may be included in the electrolyte material of the solid electrolyte layer.

[0148] In this application, unless otherwise specified, "sulfide-based electrolyte," "sulfide-based solid electrolyte," and "sulfide-based electrolyte particle" have the same meaning and may be used interchangeably. They refer to a solid electrolyte containing a sulfide electrolyte component and may be the sulfide electrolyte itself or may have a coating layer installed on the surface of the sulfide electrolyte, but are not limited thereto. The coating layer installed on the surface of the sulfide electrolyte may be an oxygen storage layer, but is not limited thereto. Non-limitingly, the sulfide-based electrolyte with the coating layer installed may be a coated electrolyte particle related to an embodiment or example of this application.

[0149] In this application, unless otherwise specified, the types of sulfide electrolyte components contained in different locations or different materials of the "sulfide solid-state battery" may be the same or different. For example, the types of sulfide electrolyte components contained in the anode layer and the solid electrolyte layer may be the same or different. The types of sulfide electrolyte components in a sulfide-based electrolyte without coated electrolyte particles and an oxygen storage layer may be the same or different.

[0150] In this application, unless otherwise specified, a “coated particle” is a solid material comprising a particle body and an oxygen storage layer located on at least a portion of the surface of the particle body. The oxygen storage layer may be located on a portion of the surface of the particle body and may completely cover the particle body. In some embodiments thereof, the coated particle comprises a particle body and an oxygen storage layer located on a portion of the surface of the particle body.

[0151] In this application, unless otherwise specified, "oxygen storage layer" refers to a layer comprising an 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.

[0152] In this application, unless otherwise specified, "oxygen storage material" refers to a material having the ability to absorb and store oxygen molecules or oxygen atoms. Unless otherwise specified, the oxygen storage material related to this application, after absorbing and storing oxygen, can essentially maintain a fixation role for the absorbed oxygen during the storage and manufacturing process of solid-state batteries and components constituting solid-state batteries, and reversible release of oxygen does not essentially occur.

[0153] In this application, unless otherwise specified, "particle body" refers to an internal solid portion of a coated particle coated with an 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, and the coating layer on the particle body itself does not contain oxygen storage material. As a non-limiting example, the anode active body among the coated anode active particles may include a coating layer.

[0154] Unless otherwise specified in this application, "located on at least a portion of the surface of solid X" indicates that it is located on at least a portion of the surface of solid X.

[0155] This solid battery material can be used as a sulfide solid battery material, and this solid battery material comprises coated particles having a surface oxygen storage layer installed thereon, wherein the oxygen storage layer is positioned on at least a portion of the surface of the coated particles; the coated particles may be positively active particles coated with a surface oxygen storage layer, may be sulfide-based electrolyte particles coated with a surface oxygen storage layer, or may be a combination of the two types of particles described above coated with a surface oxygen storage layer. When manufacturing a sulfide solid battery using this solid battery material, the probability of contact between the sulfide electrolyte and oxygen can be reduced by utilizing the oxygen absorption effect of the oxygen storage material in the oxygen storage layer, thereby improving the chemical stability of the sulfide electrolyte during the battery manufacturing process, which is advantageous for fully exercising the role of rapid ion conduction of the sulfide electrolyte, thereby promoting stable operation of the solid battery and improving the discharge capacity and cycle performance of the sulfide solid battery.

[0156] Any solid battery material, sulfide solid battery material, or sulfide all-solid battery material described in this application may be directly introduced into a manufacturing process of a solid battery, sulfide battery, or sulfide all-solid battery in solid form through a dry method, or may be introduced into a manufacturing process of a battery in a slurry form through a wet method, and then the solvent is removed through a subsequent drying process so that only the solid material among the solid battery material, sulfide solid battery material, or sulfide all-solid battery material is retained in the battery.

[0157] In some embodiments, the solid battery material is a solid material, and all of its constituent materials are solid.

[0158] In some embodiments, the solid battery material is a slurry, and its constituent materials are a solid material and a dispersion solvent, and it can be understood that the solid material in the slurry includes at least the aforementioned coated particles. Generally, the dispersion solvent is a water-insoluble solvent, and as a non-limiting example, the removable solvent may include one or more of p-xylene, trimethylbenzene, butylbutyrate, heptane, etc., and more specifically p-xylene.

[0159] In some embodiments, the solid battery material is used to form a positive electrode film or a positive electrode layer in the solid battery and may be further applied to the positive electrode layer or positive electrode film comprising a sulfide electrolyte component. Non-limitingly, the sulfide electrolyte component may be provided through coated electrolyte particles in the solid battery material and may also be provided through positive electrode electrolyte particles in the form of sulfide.

[0160] In some embodiments of the present application, coated electrolyte particles are provided. The coated electrolyte particles are the coated particles of the present application, the particle body is a solid electrolyte body, and the solid electrolyte body comprises a sulfide electrolyte.

[0161] Unless otherwise specified in this application, "coated electrolyte particles" comprise 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. Accordingly, the coated electrolyte particles are sulfide-based electrolyte particles having an oxygen storage layer installed on their surface. Non-limitingly, coated electrolyte particles may be obtained by coating an oxygen storage material onto a sulfide-based electrolyte (e.g., a sulfide electrolyte particle) that does not have an oxygen storage layer.

[0162] These coated electrolyte particles can be used as a solid electrolyte within the solid electrolyte layer of a solid-state battery, or as a solid electrolyte within the electrode active material layer (i.e., as a positive electrode electrolyte particle). For example, they can be used as a solid electrolyte within the positive electrode active material layer. When the coated electrolyte particles are used to manufacture individual solid electrolyte membranes or positive electrode membranes, or to form a positive electrode layer on a substrate (e.g., a solid electrolyte membrane), and during the process of manufacturing a solid-state battery using a membrane sheet containing these coated electrolyte particles, the oxygen storage layer installed on the surface of the coated electrolyte particles can serve to protect the sulfide electrolyte. Furthermore, it can reduce or separate the decomposition of the sulfide electrolyte by oxygen in the air, thereby improving the chemical stability of the sulfide electrolyte during the battery manufacturing process. This is advantageous for the sulfide electrolyte to fully perform its role of rapid ion conduction, which promotes stable operation of the solid-state battery and is beneficial for improving the discharge capacity and cycle performance of the sulfide solid-state battery. Furthermore, the oxygen storage layer installed on the surface of the coated electrolyte particles can reduce or separate direct contact between the sulfide electrolyte and moisture in the air, thereby suppressing the decomposition of the sulfide electrolyte and the generation of hydrogen sulfide gas, which is advantageous for improving the chemical stability of the sulfide electrolyte. Therefore, by installing an oxygen storage layer on the surface of the sulfide electrolyte, the oxygen storage material within the layer can absorb and store oxygen, and by blocking direct contact between the sulfide electrolyte and moisture, superior air stability can be imparted to the coated electrolyte particles.

[0163] In some embodiments of the present application, a coated anode-active particle is provided. The coated anode-active particle is another coated particle of the present application, the particle body is an anode-active body, and the anode-active body comprises an anode-active material.

[0164] In this application, unless otherwise specified, a “coated anode active particle” comprises an anode active body and an oxygen storage layer located on at least a portion of the surface of the anode active body, wherein the anode active body comprises an anode active material and the oxygen storage layer comprises an oxygen storage material. Accordingly, the coated anode active particle is an anode active particle having an oxygen storage layer installed on its surface. Non-limitingly, a coated electrolyte particle may be obtained by coating an oxygen storage material onto an anode active particle that does not have an oxygen storage layer.

[0165] These coated positive active particles can provide a positive active material to the positive layer of a solid-state battery, that is, they can be used as positive active particles. In the case of solid-state batteries, positive electrolyte particles are generally installed on the positive active material layer of the positive layer to perform functions such as accelerating ion conduction, reducing interfacial impedance, and maximizing the capacity of the positive active particles. When the positive electrolyte particles are sulfide-based electrolytes, i.e., contain sulfide electrolytes, the oxygen storage layer installed on the surface of the coated positive active particles can absorb and store oxygen during the manufacturing process of the positive film, the positive layer of the solid-state battery, and the solid-state battery. This can reduce or prevent the erosion and decomposition of the sulfide electrolyte caused by oxygen in the air, thereby improving the chemical stability of the sulfide electrolyte during the battery manufacturing process. This is advantageous for fully utilizing the role of rapid ion conduction of the sulfide electrolyte and reducing interfacial impedance, which can promote stable operation of the solid-state battery. Consequently, it is beneficial for improving the discharge capacity and cycle performance of the sulfide solid-state battery, and can also improve the scaling performance of the solid-state battery. Therefore, by installing an oxygen storage layer on the surface of the positive electrode active material, it can serve to protect 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, which is advantageous for improving the aforementioned electrochemical performance of the solid-state battery.

[0166] The oxygen storage material related to the embodiments or examples of the present application may use oxygen storage materials known in the art.

[0167] In some embodiments, the oxygen storage material is a "chemical oxygen storage material" that absorbs and fixes oxygen using a chemical reaction with oxygen.

[0168] The oxygen storage material may include, without limitation, one or more of lanthanide metal sulfate type oxygen storage materials, yttrium barium cobalt oxide type oxygen storage materials, and perovskite type oxygen storage materials. All of these oxygen storage materials can achieve oxygen absorption and fixation by storing oxygen (O) in the crystal lattice of the oxygen storage material. YBaCo4O 7+δ Taking (YBCO) oxygen storage materials as an example, the stoichiometric ratio of oxygen (O) elements can vary within a certain range. It stores oxygen molecules or atoms within the crystal lattice of the oxygen storage material to absorb and fix oxygen, and its oxygen storage capacity is very high, reaching 2,700 μmol O / g. As non-limiting examples, lanthanide metal sulfate-type oxygen storage materials, yttrium barium cobalt oxide-type oxygen storage materials, and perovskite-type oxygen storage materials exhibit more stable oxygen absorption and fixation effects, and no reversible release of oxygen occurs during storage and processing related to solid-state batteries and their absence. YBaCO4O7 +δ For example, if heated to a very high temperature of 200°C or higher, oxygen may be re-released.

[0169] To a limited extent, lanthanide metal sulfate-type oxygen storage materials have the chemical formula Ln2O2SO4 - δ1The oxygen storage material may include, where Ln is a lanthanide metal element, and the lanthanide metal element may include, but is not limited to, one or more of La, Ce, Pr, Nd, Sm, Eu, Gd and Tb, and 0≤δ1≤4. Without limitation, δ1 may 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 may also be selected from a range such as 0<δ1<4, 0≤δ1<4, etc.

[0170] Non-limitingly, yttrium barium cobalt oxide type oxygen storage materials have the chemical formula (Y x M1 (1-x) )(Ba y M2 (1-y) )(Co z M3 (1-z) )4O 7+δ2The oxygen storage material may include, where M1 may be selected from one or more elements among Ca, In, Dy, Ho, Er, Tm, Yb, and Lu, but is not limited thereto, M2 is Sr, and M3 may be selected from one or more elements among Mn, Fe, Ni, Cu, Zn, Al, Ga, and Zr, but is not limited thereto, and , 0≤x≤1, 0≤y≤1, 0≤z≤1, 0≤δ2≤1.5. Without restriction, x, y, and z may each independently be any one 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 may be any one 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.

[0171] Non-limitingly, perovskite-type oxygen storage materials have the chemical formula La1 - a A a Mn1 - b B b O3 -δ3The oxygen storage material may include, wherein A may be selected from one or more elements among Sr, Y, Ce, Pr, and Nd, B may be selected from one or more elements among Ni, Fe, Cu, and Co, and 0≤a≤1, 0≤b≤1, and 0≤δ3≤1. Non-limitingly, a and b may each independently be any one 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 restriction, δ3 may be any one 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.

[0172] In some embodiments, the oxygen storage material is La2O2SO4, YBaCo4O7, La 0.8 Sr 0.2 CoO3, Ce0 . 6Zr0 . 3Al0 . 101 .95 It may include one or more of the following.

[0173] In some embodiments, the weight ratio of the coated particles of the oxygen storage material (e.g., coated anode-active particles or coated electrolyte particles) may be from 0.1 wt% to 10 wt%, optionally from 0.5 wt% to 5 wt%, and may be an interval consisting of any one of the following percentages or any two percentages selected from below: 0.1 wt%, 0.2 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.6 wt%, 1.8 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 9 wt%, 10 wt% Etc. The coated particles may be coated anode-active particles or coated electrolyte particles.

[0174] 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 be a section composed of any one of the following thicknesses or any two thicknesses selected from the following: 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 among coated anode active particles and may be an oxygen storage layer among coated electrolyte particles.

[0175] In some embodiments, the coated particles satisfy one or more of the following features (any value parameter among the following features may be selected from any appropriate value or range in the context):

[0176] The weight ratio of the coated particles of the oxygen storage material (e.g., coated anode-active particles or coated electrolyte particles) is 0.1% to 10% by weight, and optionally 0.5% to 5% by weight;

[0177] The thickness of the oxygen storage layer is 0.1 nm to 50 nm, and optionally 0.5 nm to 10 nm.

[0178] It can be understood that the amount of oxygen storage material coating can be controlled by controlling any of the parameters among the weight ratio of the coated particles of the oxygen storage material and the thickness of the oxygen storage layer, and that the amount of oxygen storage material coating can also be controlled by controlling these two parameters simultaneously. By controlling at least one of the parameters among the weight ratio of the coated particles of the oxygen storage material and the thickness of the oxygen storage layer within the aforementioned range, it is advantageous not only to improve the stability of the sulfide electrolyte component involved in the solid-state battery manufacturing process, but also to fully perform the role of rapid ion conduction of the sulfide electrolyte and to reduce interfacial resistance.

[0179] Based on the stoichiometric ratio of the oxygen storage material described in this application, an oxygen storage material having a target chemical composition can be manufactured by selecting an appropriate precursor material using a method that includes, but is not limited to, existing methods in the art.

[0180] In some embodiments, a desired oxygen storage material can be manufactured by uniformly mixing a necessary precursor material, a solvent, and an optional auxiliary agent according to the stoichiometric ratio of the oxygen storage material, uniformly dispersing, ball milling, drying, performing a first sintering treatment, grinding to an appropriate particle size (e.g., 1 nm to 100 nm), and optionally performing a second sintering treatment.

[0181] For example, in the preparation of an oxygen storage material YBaCO4O7 (which can be denoted as YBCO), the precursor materials may be Y2O3, BaCO3, and Co3O4, the solvent may be an organic solvent (e.g., ethanol), no other additives may be required, and the material may be dried at 80°C until dry (a blast drying oven may be used), the atmosphere of the first sintering treatment may be air, and the first sintering treatment may be performed at 1000°C for 12 hours, and the atmosphere of the second sintering treatment may be air, and the second sintering treatment may be performed at 1100°C for 24 hours.

[0182] For example, in the preparation of a YBaCO4O7 oxygen storage material, the precursor materials may be Y2O3, BaCO3, and Co3O4, the solvent may be an organic solvent (e.g., ethanol), no other additives may be required, and the material may be dried at 80°C until dry (a blast drying oven may be used), the atmosphere of the first sintering treatment may be air, and the first sintering treatment may be performed at 1000°C for 12 hours, and the atmosphere of the second sintering treatment may be air, and the second sintering treatment may be performed at 1100°C for 24 hours.

[0183] In some embodiments, a necessary precursor material, solvent, and optional auxiliary agent may be uniformly mixed according to the stoichiometric ratio of the oxygen storage material, a composite solution may be prepared and reacted under continuous dispersion and heating conditions, the pH value of the reaction system may be controlled through a pH regulator during the reaction process, an intermediate precipitate may be produced, solid-liquid separation (e.g., suction filtration) may be performed, the solution may be washed with a neutral solution, dried, subjected to a first sintering treatment, ground to an appropriate particle size (e.g., 1 nm to 100 nm), and optionally subjected to a second sintering treatment to produce the desired oxygen storage material.

[0184] Taking the manufacture of La2O2SO4 oxygen storage material as an example, the precursor materials are La(NO3)3·6H2O and sodium dodecylsulfonate CH3(CH2) 10 CH2SO3Na may be used, the auxiliary agent may be ammonia, the continuous dispersion condition may be continuous stirring, the heating condition may be heating at 40°C for 1 hour, then raising the temperature to 50°C and stirring continuously for 10 hours, the pH of the reaction system may be 9, the atmosphere of the first sintering treatment may be air, the first sintering treatment may be performed at 550°C for 5 hours, and after grinding, a La2O2SO4 oxygen storage material may be obtained.

[0185] La0 . 8Sr0 . Taking the preparation of 2COO3 oxygen storage materials as an example, the precursor materials may be La(NO3)3·6H2O, Co(NO3)2·6H2O, and Sr(NO3)2, and the adjuvant may be urea, and the urea dosage and La0 . 8Sr0 . The theoretical yield molar ratio of 2CoO3 can be 1:(3 to 5), for example 1:4, and the reaction can be carried out under conditions of continuous stirring and heating at 80°C, the pH adjuster can be ammonia, the pH value of the reaction system can be 9, the atmosphere of the first sintering treatment can be air, and the first sintering treatment can be performed at 700°C for 5 hours, the atmosphere of the second sintering treatment can be air, and the second sintering treatment can be performed at 1050°C for 10 hours.

[0186] Ce0 . 6Zr0 . 3Al0 . 101 .95 Taking the manufacture of oxygen storage materials as an example, the precursor materials may be cerium nitrate, zirconium nitrate, and aluminum nitrate, the solvent may be water, the auxiliary agent may be urea, and the urea dosage and Ce0 . 6Zr0 . 3Al0 . 101.95 The theoretical yield molar ratio can be 1:(3 to 5), for example 1:4, and the reaction can be carried out under conditions of continuous stirring and heating at 80°C, the pH adjuster can be ammonia, the pH value of the reaction system can be 9, the atmosphere of the first sintering treatment can be air, and the first sintering treatment can be performed at 500°C for 5 hours, the atmosphere of the second sintering treatment can be air, and the second sintering treatment can be performed at 1000°C for 10 hours.

[0187] To those skilled in the art, based on the structure and chemical composition of the coated material described in this application, it can be manufactured using methods including, but not limited to, conventional particle coating methods. As a non-limiting example, a physical coating method is used. A solid oxygen storage material can be coated on at least a portion of the surface of a particle body (e.g., a positively active body or a solid electrolyte body containing a sulfide electrolyte) using a conventional physical coating method. Dry coating may be used, but is not limited thereto. Reference may also be made to the following examples. Unless otherwise specified, the oxygen storage material can be coated on at least a portion of the surface of the particle body in an inert atmosphere (e.g., an argon atmosphere).

[0188] In some embodiments, an oxygen storage material having an appropriate particle size (which may correspond to oxygen storage particles) is mixed with the particle body according to the required coating amount and heat-treated to obtain coated particles having a desired structure and chemical composition. In some embodiments, a YBCO-coated lithium transition metal oxide (e.g., lithium nickel cobalt manganese oxide, more specifically, e.g., NCM) 811 For example, in the manufacture of ), heat treatment can be performed at a temperature of 450°C for 5 hours.

[0189] In some embodiments, an oxygen storage material having an appropriate particle size (which may correspond to oxygen storage particles) is prepared as a colloidal solution, then sufficiently mixed with the particle body according to the required coating amount and heated to obtain coated particles having the desired structure and chemical composition. In some embodiments, a YBaCo4O7-coated sulfide electrolyte (e.g., Li 5.5 PS 4.5 Cl 1.5 For example, in the preparation of ), a colloidal solution can be prepared from xylene, and the heat treatment method may be vacuum drying at 120°C for 10 hours.

[0190] In some embodiments, an in situ coating can be performed on the surface of the particle body. In some of the embodiments, a reaction system comprising 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, and the pH value of the reaction system can be controlled through a pH regulator during the in situ reaction process, and after sintering the collected solid intermediate, an oxygen storage layer is formed on at least a portion of the surface of the particle body, thereby obtaining a coated particle having an oxygen storage layer. Oxygen storage material La 0.8 Sr 0.2 CoO3-coated lithium transition metal oxides (e.g., lithium nickel cobalt manganese oxide, more specifically, e.g., NCM 811 For example, in the manufacture of the oxygen storage material, the precursor materials may be La(NO3)3·6H2O, Co(NO3)2·6H2O, and Sr(NO3)2, the solvent may be water, the auxiliary agent may be hexadecyltrimethylammonium bromide, the pH adjuster may be ammonia, the pH value of the reaction system may be 9, the in-situ reaction temperature may be 80°C, and the sintering treatment conditions may include heating at 500°C for 5 hours.

[0191] In the present application, particle structure analysis methods such as transmission electron microscopy (TEM) can be used to detect and analyze whether coated particles have a coating layer, and elemental analysis methods such as energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) techniques, and inductance-coupled plasma spectroscopy (ICP) can be combined to detect and identify whether the coating layer contains oxygen storage material and the elemental type and chemical composition of the particle body, and parameters such as the thickness of the oxygen storage layer and the weight ratio or weight percentage of the oxygen storage material in the oxygen storage layer in the coated particles can also be analyzed using these methods.

[0192] In some embodiments, the coated particle (80) comprises a particle body (82) and an oxygen storage layer (84) located on the surface of the particle body (82). Refer to FIG. 1.

[0193] In some embodiments, the coated particle (80) comprises a particle body (82) and an oxygen storage layer (84) located on the surface of the particle body (82), and the oxygen storage layer (84) comprises an oxygen storage material (842). Reference may be made to FIG. 2.

[0194] In some embodiments of the present application, at least two types of coated particles (refer to FIG. 3) are provided, one being a coated anode active particle (820) and the other being a coated electrolyte particle (810); the coated anode active particle (820) comprises an anode active body (822) and an oxygen storage layer (84) located on the surface of the anode active body (822), and the oxygen storage layer (84) comprises an oxygen storage material (842); the coated electrolyte particle (810) comprises 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) comprises an oxygen storage material (842).

[0195] In some embodiments, the oxygen storage material comprises oxygen storage particles, the particle size of the oxygen storage particles is 1 nm to 100 nm, optionally 1 nm to 50 nm, and may be a section composed of any one of the following dimensions or any two dimensions selected from below: 1 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, etc.

[0196] 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.

[0197] In this application, the "particle size of oxygen storage particles" may be tested and analyzed using particle dimensional analysis methods such as a transmission electron microscope (TEM) or a laser particle size analyzer. These testing methods may also be used to test and analyze the particle dimensions of other particulate materials related to this application (e.g., coated anode active particles, coated electrolyte particles, anode active particles, particulate electrolyte materials, raw materials used to provide the particle body, etc.), such as parameters including particle size and particle size distribution, and the average values ​​of some dimensional parameters.

[0198] The oxygen storage material located in the oxygen storage layer may be particulate oxygen storage particles, and in this case, the specific surface area of ​​the oxygen storage particles can be controlled by adjusting the particle size of the oxygen storage particles. When the particle size of the oxygen storage particles is controlled within the aforementioned range, it is advantageous to allow the oxygen storage particles to have a larger oxygen absorption surface, which is advantageous for the oxygen storage material to effectively perform its role of absorbing and storing oxygen, and also advantageous for it to perform its role of blocking moisture from the air.

[0199] In some embodiments, D of the coated anodic active particles v50 is 0.1μm to 20μm, optionally 1μm to 10μm, and may be a section composed of any one of the following dimensions or any two dimensions selected from below: 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.

[0200] In the context of the present application, cumulative volume distribution particle size D v The particle size dimension of a material can be characterized using N (where N represents any value selected from 0 to 100), referring to the particle size corresponding when the cumulative volume distribution percentage of the material reaches N%, and the particle size is D v The percentage of volume less than or equal to N is N%. D v N can be obtained from the volume cumulative distribution curve of the material particle size, and unless otherwise specified, the volume cumulative distribution curve accumulates from 0 on the smaller particle size side. D v 50 is used as an example for explanation. In this application, unless otherwise specified, D v 50 refers to the particle size corresponding when the cumulative volume distribution percentage of the material reaches 50%, and this parameter is D, where D is the particle size of the particles occupying 50% of the material volume. v The particle size of the particle occupying 50% of the material volume is 50 or less, and D v Indicates that it is greater than 50. A person with ordinary knowledge in this field D vThe meaning of 50 can be understood, and measurements can be taken using instruments and methods known in the field. For example, by referring to GB / T 19077-2016 Particle Size Distribution Laser Diffraction Method, measurements can be conveniently taken using laser particle size analyzers such as the Mastersizer 2000E laser particle size analyzer from Malvern Instruments Co., Ltd., UK, or the LS-909 laser particle size analyzer (OMEC Instruments Co., Ltd.). Furthermore, for additional tests using instrument models such as the Malvern 2000 (MasterSizer 2000) laser particle size analyzer, the tests can be performed by referring to the standard procedure GB / T19077-2016 / ISO 13320:2009.

[0201] In some embodiments, the particle size of the anode active body is 0.1 μm to 20 μm, optionally 1 μm to 10 μm, and may be a section composed of any one of the following dimensions or any two dimensions selected from below: 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, 6.5 μm, 7 μm, 7.5 μm, 8 μm, 8.5 μm, 9 μm, 9.5 μm, 10 μm, 10.5 μm, 11 μm, 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.

[0202] In this application, unless otherwise specified, "particle size of the anode-active body" refers to the maximum diameter of the anode-active body in each direction.

[0203] In this application, the dimensions of a portion of the particle material, such as the "particle size of the anode active body" and the "particle size of the solid electrolyte body," may be tested and analyzed using particle structure and dimension analysis methods such as transmission electron microscopy (TEM), and may be analyzed in combination with elemental analysis methods.

[0204] In some embodiments, the coated anode-active particles satisfy at least one of the following features (any value parameter among the following features may be selected from any appropriate value or range in the context):

[0205] D of coated positively active particles v 50 is 0.1 μm to 20 μm, and optionally 1 μm to 10 μm—wherein, D v 50 indicates the corresponding particle size when the cumulative volume distribution percentage of the multi-particle mixture reaches 50%.

[0206] The particle size of the positively active body is 0.1 μm to 20 μm, and optionally 1 μm to 10 μm.

[0207] D of coated positively active particles v The dimensional size of the coated anode active particles can be controlled by controlling at least one of the particle size of 50 and the anode active body. D of the coated anode active particles vBy controlling at least one parameter of the particle size of the anode active body within the range described above, it is advantageous to improve the discharge capacity of the coated anode active particles and maintain good contact between the coated anode active particles and the sulfide-based electrolyte in the composite anode. The active ion transport pathways inside the coated anode active particles having smaller dimensions are shorter, which is advantageous for improving the discharge capacity of the coated anode active particles themselves; the coated anode active particles having larger dimensions can be better coated by the sulfide-based electrolyte and have better interfacial contact with the sulfide-based electrolyte, which is advantageous for the cycle performance of the battery. Coated anode active particles with relatively moderate dimensions can enable the battery to achieve both high discharge capacity and excellent cycle performance.

[0208] Oxide cathode active materials, such as lithium transition metal oxides, and furthermore, high-nickel cathode active materials, high-voltage lithium cobalt oxides, 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, when these oxide cathode active materials come into direct contact with the sulfide electrolyte, elemental interdiffusion and chemical reactions occur spontaneously, creating a thicker interfacial impedance layer and increasing the interfacial impedance, which affects the performance of the solid-state battery. Additionally, if the cathode active material among the cathode active particles includes an oxide cathode active material (e.g., lithium transition metal oxide), the oxide cathode active material can release oxygen under high-voltage operating conditions (e.g., greater than 4.2V, and furthermore, charged to the high-voltage region during the initial cycle), which further attacks the sulfide solid electrolyte and causes decomposition of the sulfide solid electrolyte. When oxidative decomposition of sulfide solid electrolytes occurs, the interfacial impedance increases, which actually affects the development of discharge capacity and degrades the electrochemical performance of the battery.

[0209] In some embodiments, the anode active material among the coated anode active particles comprises an oxide anode active material. In some embodiments thereof, the oxide anode active material may comprise, but is not limited to, a lithium transition metal oxide.

[0210] In this application, unless otherwise specified, "oxide anode active material" has the meaning known in the art and refers to an anode active material in the form of an oxide.

[0211] In this application, unless otherwise specified, "lithium transition metal oxide" has the meaning known in the art and refers to an anode active material comprising a transition metal element and a lithium element. A lithium transition metal oxide is an oxide anode active material.

[0212] By installing the aforementioned solid battery material on a positive electrode active material layer containing an oxide positive electrode active material (e.g., lithium transition metal oxide), direct contact between the oxide positive electrode active material and the sulfide electrolyte can be prevented, and oxygen released from the positive electrode can be absorbed through an oxygen storage material to suppress the attack of the released oxygen on the sulfide electrolyte, thereby further reducing the oxidative decomposition of the sulfide electrolyte by oxygen, suppressing interfacial side reactions between the oxide positive electrode active material (e.g., lithium transition metal oxide) and the sulfide electrolyte, and suppressing the increase in interfacial impedance. This is advantageous for improving the stability of the sulfide electrolyte within the positive electrode layer during the cycling process of the sulfide solid battery, thereby maintaining excellent conductivity, allowing the ionic conduction of the sulfide electrolyte to be exerted over the long term, and allowing the capacity of the positive electrode active particles to be fully exerted, thereby providing excellent high voltage stability to the sulfide solid battery. Additionally, the sulfide solid battery can be made to have higher initial Coulomb efficiency, higher discharge capacity, higher magnification performance, and better cycle performance. In addition, after a specific concentration of oxygen is stored in the oxygen storage material, the partial pressure of oxygen on the surface of the anode active particles increases, further hindering the release of oxygen from the anode active particles, thereby enhancing the structural stability of the anode material.

[0213] In some embodiments, during the heat treatment process of the surface coating (e.g., 400°C to 600°C), the oxygen storage material can remove some crystal lattice oxygen from the positive active material and form oxygen vacancy sites on the surface of the positive active particle by coming into close contact with the positive material, and the oxygen vacancy sites on the surface of the positive active particle can promote electron and ion transport on the surface of the positive active particle, thereby further improving the electrochemical performance of the solid-state battery.

[0214] When the positive active material among the positive active particles includes an oxide positive active material (e.g., a lithium transition metal oxide), at least one parameter among the weight ratio of the coated particles of the oxygen storage material and the thickness of the oxygen storage layer can be controlled (e.g., the weight ratio of the coated particles of the oxygen storage material (e.g., coated positive active particles or coated electrolyte particles) can be controlled to 0.1 wt% to 10 wt%, optionally to 0.5 wt% to 5 wt%, and the thickness of the oxygen storage layer can be controlled to 0.1 nm to 50 nm, optionally to 0.5 nm to 10 nm), thereby allowing for the suppression of oxygen release and good interfacial ion transport to be considered together. This not only allows for the suppression of oxygen release and the improvement of the stability of the sulfide electrolyte to achieve good discharge capacity and cycle performance, but also allows for the full utilization of the discharge capacity of the positive layer by achieving good interfacial ion transport.

[0215] When the anode active material among the anode active particles includes an oxide anode active material (e.g., a lithium transition metal oxide), D of the coated anode active particles v By controlling at least one of the particle size of 50 and the anode active body, the amount of oxygen storage material in the oxygen storage layer relative to the anode active material contained within the anode active complement may also be indirectly controlled. D of the coated anode active particle v By controlling at least one parameter of the particle size of the anode active body within the range described above, the oxygen storage material is not only advantageous for providing sufficient oxygen absorption capacity, but also for improving the discharge capacity of the coated anode active particles and maintaining good contact between the coated anode active particles and the sulfide-based electrolyte in the composite anode.

[0216] Non-limitingly, the weight percentage of the oxide cathode active material (e.g., lithium transition metal oxide) in the cathode active body may be 50 wt% or more (i.e., ≥50 wt%), furthermore 60 wt% or more, furthermore 80 wt% or more, furthermore 90 wt% or more, furthermore 95 wt% or more, and furthermore 100 wt% or more. The weight percentage of the oxide cathode active material (e.g., lithium transition metal oxide) in the cathode active body may be any one of the following weight percentages or an interval consisting of any two weight percentages selected from the following: 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 72 wt%, 74 wt%, 75 wt%, 76 wt%, 78 wt%, 80 wt%, 82 wt%, 84 wt%, 85 wt%, 86 wt%, 88 wt%, 90 wt%, 92 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, 100 wt%, etc.

[0217] In some embodiments, the oxide cathode active material (e.g., lithium transition metal oxide) comprises one or more of a lithium cobalt oxide type cathode active material, a high nickel cathode active material, a lithium-rich manganese-based cathode active material, and a modified form of any of the above-mentioned cathode active materials, and the modified form may include one or more of doping modification and coating modification.

[0218] It can be understood that the lithium cobalt oxide type cathode active material contains the elements Li, Co, and O.

[0219] In some embodiments, the atomic molar ratio of the Co element and the O element is x2:2, satisfying 0.9 ≤ x2 ≤ 1. x2 may be any one 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.

[0220] In some embodiments, the atomic molar ratio of the Co element and the Li element is x2, satisfying 0.9 ≤ x2 ≤ 1. x2 may be any one 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.

[0221] Non-limitingly, the lithium cobalt oxide type cathode active material may comprise Li, Co, and O elements with an atomic molar ratio of 1:x2:2, satisfying 0.9 ≤ x2 ≤ 1. Non-limitingly, x2 may be any one 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.

[0222] In some embodiments, the lithium cobalt oxide type cathode active material has the chemical formula LiCo x2 R 1-x2 It includes a lithium transition metal oxide of O2, where R can be selected from one or more elements among Ni, Mg, Ti, Al, Cr, Fe, Nb, and Ta.

[0223] It can be understood that the high-nickel cathode active material contains the elements Li, Ni, and O.

[0224] In some embodiments, the atomic molar ratio of Ni and O is y2:2 and satisfies 0.6 ≤ y2 ≤ 1. Non-limitingly, y2 may be any one 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. Non-limitingly, y2 may be selected from any range such as 0.8 ≤ y2 ≤ 1.

[0225] In some embodiments, the atomic molar ratio of Ni and Li is y2, satisfying 0.6 ≤ y2 ≤ 1. Non-limitingly, y2 may be any one 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. Non-limitingly, y2 may be selected from any range such as 0.8 ≤ y2 ≤ 1.

[0226] Non-limitingly, the high-nickel cathode active material may include Li, Ni, and O elements with an atomic molar ratio of 1:y2:2 and satisfy 0.6 ≤ y2 ≤ 1. Non-limitingly, y2 may be any one 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. Non-limitingly, y2 may be selected from any range such as 0.8 ≤ y2 ≤ 1.

[0227] In some embodiments, the high-nickel cathode active material contains not only nickel (Ni) elements but also cobalt (Co) elements and D elements, wherein D elements may be one or two of manganese (Mn) elements and aluminum (Al) elements. In this case, the atomic number of nickel elements relative to lithium elements is y2. In some embodiments thereof, y2 ≥ 0.6; further optionally, y2 ≥ 0.8; and further optionally, y2 ≥ 0.9. y2 may be any one of the following values, or one or more of the following values ​​that are less than 1, or an interval consisting of any two of the following values: 0.6, 0.7, 0.8, 0.9, 0.93, etc. y2 can 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.

[0228] In some embodiments, the high-nickel anode active material has the chemical formula LiNi y2 Co z2 D 1-y2-z2It comprises a lithium transition metal oxide of O2, wherein 0 ≤ z2 ≤ 0.4 and 0.6 ≤ (y2+z2) ≤ 1, and D may be selected from one or more elements selected from Mn, Al, Zr, La, Ce, Ti, Mg, Nb, Ta, Mo, and W. In some embodiments, D comprises one or two of the elements Mn and Al, and additionally, D is optionally either the Mn element or the Al element. In some embodiments thereof, D comprises the element Mn, and additionally, D is optionally the element Mn. Non-limitingly, z2 may be any one 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.

[0229] Non-limitingly, lithium-rich manganese-based cathode active materials include Li, Mn, and O elements with an atomic molar ratio of (1+p):(p+r(1-p)):(2+p) and 0 <p≤1, 0≤r≤1을 충족한다. 비제한적으로, p는 하기 값 중 어느 하나이거나 하기 중 임의 2개의 값으로 구성된 구간 또는 0보다 크고 하기 임의의 값 이하인 값일 수 있다: 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 등. 비제한적으로, r은 하기 값 중 어느 하나이거나 하기 중 임의 2개의 값으로 구성된 구간일 수도 있다: 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 등. p는 0.2≤p≤1 임의의 범위에서 선택할 수도 있다.

[0230] In some embodiments, the lithium-rich manganese-based cathode active material comprises a lithium transition metal oxide having the chemical formula pLi2MnO3·(1-p)LiZO2, wherein Z may be selected from one or more elements among nickel (Ni), cobalt (Co), manganese (Mn), chromium (Cr), iron (Fe), aluminum (Al), niobium (Nb), molybdenum (Mo), and ruthenium (Ru), but is not limited thereto.

[0231] Lithium transition metal oxides, such as lithium cobalt oxide-type cathode active materials, high-nickel cathode active materials, and lithium-rich manganese-based cathode active materials, readily release oxygen under high-voltage operating conditions. When using such lithium transition metal oxides as the cathode active material among cathode active particles, installing the aforementioned solid battery material in the cathode active material layer is advantageous for considering both high energy density and long cycle performance of sulfide solid batteries under conditions where oxygen release from the cathode is possible.

[0232] When a solid battery material installed in a positive electrode active material layer includes the aforementioned coated positive electrode active particles, additionally, it is advantageous for suppressing oxygen release from the positive electrode material, improving the crystal structural stability of the positive electrode active particles during battery cycling, and suppressing the formation of surface rock salt phases, thereby enabling sufficient positive electrode capacity and improving the long-cycle performance of the battery.

[0233] In some embodiments, D of the coated electrolyte particles v 50 is 1 nm to 20 μm, optionally 50 nm to 5 μm, and may be an interval composed of any one of the following dimensions or any two dimensions selected from below: 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, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm, 8.5 μm, 9 μm, 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.

[0234] In some embodiments, the particle size of the solid electrolyte body is 1 nm to 20 μm, optionally 50 nm to 5 μm, and may be a section composed of any one of the following dimensions or any two dimensions selected from below: 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, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm, 8.5 μm, 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.

[0235] In some embodiments, the coated electrolyte particles satisfy at least one of the following features (any value parameter among the following features may be selected from any appropriate value or range in the context):

[0236] D of coated electrolyte particles v 50 is 1 nm to 20 μm, and optionally 50 nm to 5 μm—wherein, D v 50 indicates the corresponding particle size when the cumulative volume distribution percentage of the multi-particle mixture reaches 50%.

[0237] The particle size of the solid electrolyte body is 1 nm to 20 μm, and optionally 50 nm to 5 μm.

[0238] D of coated electrolyte particles v The dimensional size of the coated electrolyte particles can be controlled by controlling at least one of the particle size of 50 and the solid electrolyte body. D of the coated electrolyte particles vBy controlling at least one of the particle sizes of the solid electrolyte body and the coated electrolyte particles within the aforementioned range, it is advantageous to improve the overall ion conductivity of the membrane layer where the coated electrolyte particles are located, and to provide a superior electrical contact network, while also considering manufacturing costs and controlling the manufacturing cost of the solid electrolyte body and the amount of oxygen storage material required to manufacture the coated electrolyte particles. A relatively small particle size of the coated electrolyte particles is advantageous for improving electrical contact between positive active particles within the positive membrane or positive layer, thereby further promoting the capacity development of the solid-state battery. A relatively moderate particle size of the coated electrolyte particles is easier to manufacture.

[0239] 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-phosphorus pentasulfide complex-type sulfide electrolyte.

[0240] Unless otherwise specified, argyrodite-type sulfide electrolytes have an argyrodite-type crystalline phase structure. Non-limitingly, argyrodite-type sulfide electrolytes have the chemical formula Li6 ± s P1 - j A j S5 ±s- t B t X1 ± s It may include a phosphorus sulfide electrolyte, where 0≤j<1, 0≤t<1, 0≤s<1, and A may be selected from one or more elements among Ge, Si, Sn and Sb, but is not limited thereto, B may be one or more elements among O, Se and Te, and X may be selected from one or more elements among Cl, Br, I and F.

[0241] Unless otherwise specified, LGPS-type sulfide electrolytes have an LGPS-type crystalline phase structure. Non-limitingly, LGPS-type sulfide electrolytes have the chemical formula Li 10 ± δ5 Ge1 - g G g P2 - q Q q S 12 - w W w It may contain a phosphorus sulfide electrolyte, where 0≤δ5<1, 0≤g≤1, 0≤q≤2, 0≤w<1, G is selected from one or two elements among Si and Sn, Q is Sb, and W is selected from one or more elements among O, Se, Te, Cl, Br, I and F.

[0242] Non-limitingly, lithium sulfide-phosphorus pentasulfide complex sulfide electrolytes include (100-uv)Li2S·uP2S5·vM m N n It may contain phosphorus sulfide electrolytes, where 0 <u<100, 0≤v<100, 0≤u+v<100, 0≤m<4, 0≤n<6이고, M은 Li, B, Ge, Si, Sn 및 Sb 중 하나 이상의 원소에서 선택될 수 있지만 이에 한정되지 않고, N은 S, Se, Te, O, Cl, Br, I 및 F 중 하나 이상의 원소에서 선택될 수 있다.

[0243] By using the aforementioned solid-state battery material, sulfide electrolytes having a high ion transport rate can be used more flexibly in sulfide solid-state batteries, thereby significantly reducing the limitations on material selection for sulfide electrolytes.

[0244] In some embodiments, the sulfide electrolyte in the coated electrolyte particles may comprise at least one of a binary sulfide solid system and a ternary sulfide solid system. Non-limitingly, the binary sulfide solid system may comprise one or more of Li2S-P2S5, Li2S-SiS2, Li2S-GeS2, and Li2S-B2S3. Non-limitingly, the ternary sulfide solid system may comprise one or more of an argyrodite-type sulfide electrolyte, a Li2S-MeS2-P2S5-ternary sulfide electrolyte, a lithium germanium phosphulose-type sulfide electrolyte, a Li2S-P2S5-MS-ternary sulfide electrolyte, a Li2S-P2S5-MCl-ternary sulfide electrolyte, and a thio-LISICON-type sulfide electrolyte; Here, Me may include one or more elements among silicon (Si), germanium (Ge), tin (Sn), and aluminum (Al), and furthermore may be selected from one or more elements among Si, Ge, Sn, and Al; and M may include one or more elements among Ge, Al, Sn, lead (Pb), antimony (Sb), Si, and arsenic (As), and furthermore may be selected from one or more elements among Ge, Al, Sn, Pb, Sb, Si, and As.

[0245] In some embodiments, the solid-state battery material is a sulfide solid-state battery material. For the definition of "sulfide solid-state battery material," refer to the foregoing.

[0246] In some embodiments, the solid-state battery material is a sulfide all-solid-state battery material. For the definition of "sulfide all-solid-state battery material," refer to the foregoing.

[0247] In a second aspect of the present application, a positive active material layer comprising the solid battery material described in the first aspect of the present application is provided.

[0248] As a non-limiting example, the positive active material layer may exist in an independent positive film sheet or in the positive layer of a solid-state battery.

[0249] It can be understood that the positive active material layer provided in the second aspect of the present application comprises at least one of coated positive active particles and coated electrolyte particles. When this positive active material layer is applied to a sulfide solid-state battery, the probability of contact between the sulfide electrolyte and oxygen can be reduced by utilizing the oxygen absorption effect of the oxygen storage material in the oxygen storage layer, thereby improving the chemical stability of the sulfide electrolyte during the battery manufacturing process. This is advantageous for fully utilizing the role of rapid ion conduction of the sulfide electrolyte, thereby promoting stable operation of the solid-state battery and improving the discharge capacity and cycle performance of the sulfide solid-state battery. Additionally, the oxygen storage layer installed on the surface of the coated electrolyte particles can reduce or separate direct contact between the sulfide electrolyte and moisture in the air, thereby suppressing the decomposition of the sulfide electrolyte and the generation of hydrogen sulfide gas, which is advantageous for improving the chemical stability of the sulfide electrolyte.

[0250] As previously defined, the positive active material layer comprises at least positive active particles, and the positive active particles comprise a positive active material. In some embodiments, the positive active material among the positive active particles comprises an oxide positive active material, and additionally, the oxide positive active material comprises a lithium transition metal oxide.

[0251] Non-limitingly, the oxide cathode active material (e.g., a lithium transition metal oxide) among the cathode active materials may include, but is not limited to, a lithium transition metal oxide that can be used as a cathode active material for a solid-state battery known in the art. 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 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.; and non-limiting examples of lithium nickel cobalt manganese oxide may include LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2 (NCM 333 It may also be abbreviated as), LiNi0 . 5Co0 . 2Mn0 . 3O2(NCM 523 It may also be abbreviated as), LiNi0 . 5Co0 . 25 Mn0 . 25 O2(NCM 211 (may be abbreviated as), LiNi0 . 6Co0 . 2Mn0 . 2O2(NCM 622 (may be abbreviated as), LiNi0 . 8Co0 . 1Mn0 . 102(NCM 811 It may include (which may be abbreviated as ). Non-limiting examples of lithium nickel cobalt aluminum oxide are LiNi0 . 80 Co0 . 15Al0 . 05 It may contain O2.

[0252] Taking a solid-state battery in which the active ion is a lithium ion as an example, it can be understood that the charging and discharging process of the battery involves the desorption and consumption of lithium (Li), and that the content of Li in the anode layer (including the anode film in the context) varies when the battery is discharged in different states. In the exemplary description of the anode active material of this application, unless otherwise specified, the content of Li may be the initial state of the material or the non-initial state after charge-discharge cycles. When the anode active material is applied to the anode layer of a solid-state battery system and undergoes charge-discharge cycles, the content of Li in the anode active material contained in the anode layer generally changes. Here, the content of Li may be quantified as an atomic molar content, but is not limited thereto. Regarding "the content of Li is the initial state of the material," the initial state of the material refers to the state before it is supplied to the anode layer. A new material or new substance obtained through appropriate modification based on the listed cathode active materials falls within the scope of the cathode active materials, and the aforementioned appropriate modification refers to an acceptable modification method for the cathode active materials, and it should be understood that non-limiting examples include, for instance, coating modification. In the exemplary description of the cathode active materials in this application, the oxygen (O) content is generally a theoretical state value, and crystal lattice oxygen emission changes the atomic molar content of oxygen, causing the actual O content to fluctuate. Here, the O content can be quantified as an atomic molar content, but is not limited thereto.

[0253] In some embodiments, except that the positive electrode active material comprises an oxide positive electrode active material (e.g., a lithium transition metal oxide), it may also comprise other positive electrode active materials known in the art that can be used as solid-state batteries. As a non-limiting example, other positive electrode active materials that can be used as solid-state batteries may comprise one or more materials selected from lithium-containing phosphates of an olivine structure and modified compounds thereof. However, the present application is not limited to these materials, and other conventional materials that can be used as positive electrode active materials for solid-state batteries may also be used. Such positive electrode active materials may be used individually or in combination of two or more types. Non-limiting examples of lithium-containing phosphates of an olivine structure may include, but are not limited to, one or more of lithium iron phosphate, lithium iron phosphate and carbon composite materials, lithium manganese phosphate, lithium manganese phosphate and carbon composite materials, lithium iron manganese phosphate, and lithium iron manganese phosphate and carbon composite materials. An example of lithium iron phosphate is, for example, LiFePO4 (which may be abbreviated as LFP). An example of lithium manganese phosphate is LiMnPO4.

[0254] In some embodiments, the lithium transition metal oxide comprises 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, a lithium-rich manganese cathode active material (definitions may be referenced below), and a modified form of any of the aforementioned cathode active materials; the modified form may include one or more of doping modification and coating modification.

[0255] It can be understood that the positive active material layer comprises positive active particles. Non-limitingly, the weight ratio of positive active particles in the positive active material layer is 70% to 99% by weight, and optionally 80% to 95% by weight. Non-limitingly, the weight ratio of positive electrolyte particles in the positive active material layer may be 0.1% to 30% by weight, and optionally 5% to 20% by weight.

[0256] In some embodiments, the anode active particles comprise coated anode active particles. Non-limitingly, the weight ratio of the coated anode active particles in the anode active material layer may be 70 wt% to 99 wt%, and optionally 80 wt% to 95 wt%. The weight ratio of the coated anode active particles in the anode active material layer may be a range consisting of any one of the following weight percentages or any two weight percentages selected from below: 70 wt%, 72 wt%, 74 wt%, 75 wt%, 76 wt%, 78 wt%, 80 wt%, 82 wt%, 84 wt%, 85 wt%, 86 wt%, 88 wt%, 90 wt%, 92 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, etc.

[0257] In some embodiments, the anode electrolyte particles include a sulfide-based electrolyte.

[0258] The sulfide electrolyte contained in the sulfide-based electrolyte has excellent ion conductivity, and by installing the sulfide-based electrolyte in the anode layer, the charge transfer efficiency between the anode active material and the external environment and the sufficient release of its capacity can be better promoted.

[0259] In some embodiments, the anode active material layer includes anode electrolyte particles.

[0260] In some embodiments, the anode electrolyte particles comprise coated electrolyte particles. In this case, the anode active material layer comprises a sulfide-based electrolyte. Non-limitingly, the weight ratio of the coated electrolyte particles in the anode active material layer may be 0.1% to 30% by weight, and optionally 5% to 20% by weight. The weight ratio of the coated electrolyte particles in the anode active material layer may be any one of the following weight percentages or a range consisting of any two weight percentages selected from below: 0.1 wt%, 0.2 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.6 wt%, 1.8 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 12 wt%, 14 wt%, 15 wt%, 16 wt%, 18 wt%, 20 wt%, 22 wt%, 24 wt%, 25 wt%, 26 wt%, 28 wt%, 30 wt%, etc.

[0261] In some embodiments, the anode active material layer comprises anode active particles and anode electrolyte particles.

[0262] In some embodiments, the positive active material layer satisfies at least one of the following features (any value parameter among the following features may be selected from any appropriate value or range in the context):

[0263] In some embodiments, the anode active particles comprise coated anode active particles, wherein the weight ratio of the coated anode active particles in the anode active material layer is 70% to 99% by weight, and optionally 80% to 95% by weight;

[0264] The anode electrolyte particles comprise coated electrolyte particles, wherein the weight ratio of the coated electrolyte particles in the anode active material layer is 0.1% to 30% by weight, and optionally 5% to 20% by weight.

[0265] By controlling the weight ratio of coated anode active particles in the anode active material layer within the aforementioned range, it is advantageous to consider both high energy density and cycle stability.

[0266] When the anode film contains a sulfide-based electrolyte, controlling the weight ratio of coated anode active particles in the anode active material layer within the aforementioned range is also advantageous for achieving a combination and balance between high energy density and reduced oxidative decomposition of the sulfide electrolyte contained in the sulfide-based electrolyte.

[0267] The weight percentage of coated electrolyte particles in the anode active material layer can be controlled within the aforementioned range, which is advantageous for enabling the anode film to provide superior overall ion conductivity.

[0268] In some embodiments, the positive active material layer comprises at least positive active particles and positive electrolyte particles, the positive active particles comprise a positive active material, and the positive electrolyte particles comprise a sulfide-based electrolyte, and the positive active material and the sulfide-based electrolyte in the positive active material layer are separated by an oxygen storage layer. This oxygen storage layer may be located on the surface of at least one of the positive active particles or positive electrolyte particles, may be located only on the surface of the positive active particles (corresponding to the coated positive active particles), may be located only on the surface of the positive electrolyte particles (corresponding to the coated electrolyte surface), or may be located simultaneously on the surfaces of the positive active particles and the positive electrolyte particles. Refer to FIGS. 4 to 8.

[0269] In some embodiments, the positive active material layer (220) comprises coated electrolyte particles (810) and may be denoted as the positive active material layer (220a). Refer to FIG. 4.

[0270] In some embodiments, the positive active material layer (220) comprises coated positive active particles (820) and may be recorded as the positive active material layer (220b). Refer to FIG. 5.

[0271] In some embodiments, the positive active material layer (220) comprises coated electrolyte particles (810) and coated positive active particles (820), and may be recorded as a positive active material layer (220c). Refer to FIG. 6.

[0272] In some embodiments, the positive active material layer (220) comprises coated positive active particles (820) and a sulfide-based electrolyte (910) without an oxygen storage layer, and may be denoted as the positive active material layer (220d). Refer to FIG. 7.

[0273] In some embodiments, the positive active material layer (220) comprises a coated electrolyte particle (810) and a positive active particle (920) without an oxygen storage layer, and may be denoted as the positive active material layer (220e). Refer to FIG. 8.

[0274] In some embodiments, the anode active material layer comprises a conductive agent (which may be referred to as an anode conductive agent). As a non-limiting example, the anode conductive agent may be a carbon conductive agent. Non-limitingly, the carbon conductive agent may comprise one or more of superconducting carbon, acetylene black, carbon black, ketjen black, carbon quantum dots, carbon nanotubes, graphene, and carbon nanofibers. In some embodiments, the anode conductive agent may comprise, but is not limited to, one or more of SP, KS-6, acetylene black, ketjen black ECP having a branched structure, SFG-6, vapor-grown carbon fiber VGCF, carbon nanotubes (CNT), and graphene. Non-limitingly, the weight percentage of the anode conductive agent in the anode active material layer may be 0 to 10 weight% based on the total weight of the anode active material layer, more specifically 0 to 8 weight%, more specifically 0 to 5 weight%, and more specifically 0.1 weight% to 3 weight%. The weight percentage of the positive conductive agent in the positive active material layer may be 0.1% to 5% by weight, 0.2% to 5% by weight, 0.5% to 5% by weight, or 0.1% to 3% by weight. When manufacturing the positive material into the positive active material layer using a dry method, the positive conductive agent can be installed in the positive material, thereby improving the electronic conductivity of the positive active material layer.

[0275] In some embodiments, the anode active material layer optionally comprises an adhesive. As a non-limiting example, the adhesive may comprise one or more of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), 1,1-fluoroethylene-tetrafluoroethylene-propylene ternary copolymer, 1,1-fluoroethylene-hexafluoropropylene-tetrafluoroethylene ternary copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluorine-containing acrylate resin. Generally, the weight percentage of the adhesive in the anode active material layer may be 0 to 10 weight% based on the total weight of the anode active material layer, more specifically 0 to 8 weight%, more specifically 0.1 weight% to 5 weight%, and more specifically 1 weight% to 5 weight%. When preparing an anode material into an anode slurry using a wet method and then preparing an anode active material layer, an adhesive can be installed in the anode slurry, which can assist in film formation and is also advantageous for promoting the formation of a good electrical contact network between active particles of the anode active material layer.

[0276] Non-limitingly, the anode active material layer may include anode active particles, anode electrolyte particles, anode conductive agent, and adhesive. The type and content of each component may be referenced in the context of this application.

[0277] In the present application, unless otherwise specified, a sample of the positive active material layer in a solid-state battery may be obtained in the following manner: the battery may be disassembled to obtain a sample of the active material layer of the electrode sheet, and furthermore, the sample of the active material layer may be analyzed in the following manner: the three-dimensional structure of the sample may be reconstructed using the nano-spatial dynamic resolution and layer-by-layer cutting techniques of FIB-SEM, and the distribution and ratio of each element may be obtained by combining EDS elemental energy dispersive spectroscopy, and finally, parameters such as the composition and thickness of each structural layer of the active material layer may be obtained through quantitative analysis using software.

[0278] In the present application, unless otherwise specified, the type and content of components such as positive active particles (including coated positive active particles) and positive electrolyte particles (including coated electrolyte particles) in the positive active material layer of a solid-state battery can be detected by the following method: the structure and component analysis of the positive active material layer can be tested and analyzed using focused electron beam (FIB) technology, scanning electron microscopy (SEM), and elemental analysis technology, for example, by combining cryogenic focused electron beam (FIB) continuous cutting, cross-sectional SEM shape observation, elemental energy dispersive spectroscopy (EDS), and three-dimensional reconstruction analysis software. For example, a cryogenic focused ion beam (FIB) can be used to finely slice a sample layer by layer along the transverse direction at various thickness positions (minimum scale at the nanometer level) to separate samples of different thicknesses and positions, and scanning electron microscope (SEM) can be used to analyze the morphology, structure, and elemental distribution of the cross-sections of each layer during the continuous FIB slice process. In combination with 3D structural reconstruction software, the 3D structure of the sample can be reconstructed, and the mass and / or volume of different regions of the sample to be tested can be estimated. As a non-limiting example, test analysis for the aforementioned parameters can be performed using the FEI Scios 2HiVac instrument.

[0279] In the present application, unless otherwise specified, the particle size and particle size distribution of each solid particle in a sample of the positive active material layer of a solid battery can be analyzed in the following ways, and this may include the analysis of the particle size and particle size distribution of particle components such as positive active particles and positive electrolyte particles: In the present application, unless otherwise specified, a two-dimensional image labeled with different colors for different components can be obtained by combining an EDS test using FIB-SEM, particle components such as positive active particles and positive electrolyte particles can be distinguished according to the type of component, and the particle size and particle size distribution of particle components such as positive active particles and positive electrolyte particles can be analyzed using software embedded in the EDS instrument.

[0280] In a third aspect of the present application, an anode film comprising an anode active material layer is provided, wherein the anode active material layer comprises a solid battery material as described in the first aspect of the present application, or the anode active material layer is an anode active material layer as described in the second aspect of the present application.

[0281] Non-limitingly, the anode film may be an independent anode sheet and further used to assemble a solid-state battery; the anode film may be an anode film layer existing within a multilayer composite structure, for example, a film may be formed by pressing the constituent material of the anode film layer onto the surface of a solid electrolyte layer. As a non-limiting example, the anode film may be an anode layer or a part of an anode layer of a solid-state battery.

[0282] In this application, unless otherwise specified, "anode film" refers to a film that can be used as an anode of a solid-state battery, comprising at least an anode active material layer and generally comprising an anode current collector. This anode film comprises the anode active material layer described in the second aspect of this application.

[0283] In some embodiments, the anode film comprises an anode current collector and an anode active material layer installed on at least one surface of the anode current collector, and the definition of the anode active material layer may refer to the above.

[0284] In some embodiments, reference may be made to FIG. 13, and the anode film (20) includes an anode current collector (210) and an anode active material layer (220) located on one side of the anode current collector (210).

[0285] In some embodiments, reference may be made to FIG. 14, and the anode film (20) includes an anode current collector (210) and a positive active material layer (220) located on both sides of the anode current collector (210).

[0286] Non-limitingly, the thickness of the anode active material layer in the anode film or anode layer is 30 μm to 400 μm, optionally 60 μm to 130 μm, and may be a section composed of any one of the following thicknesses or any two thicknesses selected from the following: 30 μm, 40 μm, 50 μm, 60 μm, 80 μm, 100 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 180 μm, 200 μm, etc. The thickness of the positive active material layer can be selected from any of the following ranges: 40μm to 400μm, 40μm to 300μm, 40μm to 200μm, 40μm to 150μm, 40μm to 130μm, 40μm to 120μm, 50μm to 400μm, 50μm to 300μm, 50μm to 200μm, 50μm to 150μm, 50μm to 130μm, 50μm to 120μm, 60μm to 400μm, 60μm to 300μm, 60μm to 200μm, 60μm to 150μm, 60μm to 120μm, 80μm to 400μm, 80μm to 300μm, 80μm to 200μm, 80μm to 150μm, 80μm to 120μm, 100μm to 200μm, 120μm to 260μm, etc.

[0287] In this application, unless otherwise specified, the "thickness of the anode active material layer" in the anode film refers to the total thickness of the anode film. When an anode active material layer is installed on both sides of the anode current collector, the thickness of the anode active material layer refers to the sum of the thicknesses on both sides.

[0288] As a non-limiting example, the positive current collector has two surfaces opposite in its own thickness direction, and a positive active material layer is installed on either or both of the two surfaces opposite the positive current collector.

[0289] In some embodiments, the positive current collector may use a metal foil or a composite current collector. For example, aluminum foil may be used as the metal foil. In the positive current collector, the composite current collector may include a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. In the positive current collector, the composite current collector may be obtained by forming a metal material on a polymer material substrate. In the positive current collector, non-limiting examples of this metal material may include at least one of aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver, and silver alloy. In the positive current collector, non-limiting examples of this polymer material substrate may include one or more of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.

[0290] The anode film can be manufactured using a dry or wet method. For example, the film can be formed using a dry pressing process. Additionally, the film can be formed through, for example, wet coating and drying.

[0291] In some embodiments, an anode film sheet (the anode film sheet may be used as an anode sheet) may be manufactured in the following manner: each of the above-described components used in manufacturing the anode film sheet, e.g., anode active particles, anode electrolyte particles, anode conductive agent, adhesive, and any other component, is dry-mixed, and then the uniformly mixed material is heated and pressed to form a bulk material, and hot-rolled to form a self-standing anode sheet, and the self-standing anode sheet is hot-rolled to form a composite with an anode current collector, and the self-standing anode sheet is combined with at least one side (one side or both sides) of the anode current collector to obtain an anode film sheet. Non-limitingly, dry mixing may be performed using a dual planetary mixer. Non-limitingly, the material may be formed by heating and pressing using an internal mixer. Non-limitingly, the hot-rolling temperature may be 75°C to 85°C, and furthermore, e.g., 78°C, 80°C, 82°C, etc. A solid-state battery assembly method using a positive electrode sheet can be suitable for industrial mass production.

[0292] In some embodiments, an anode film sheet can be manufactured in the following manner: an anode slurry is formed by dispersing each of the above-described components used in manufacturing the anode film sheet, e.g., anode active particles, anode electrolyte particles, anode conductive agent, adhesive, and any other components, in an organic solvent. Additionally, an anode film sheet can be obtained by coating the anode slurry onto at least one surface of an anode current collector and undergoing processes such as drying and cold pressing. Cold pressing can be performed using a cold rolling mill. The type of organic solvent in the anode slurry may include one or more of p-xylene, trimethylbenzene, butylbutyrate, heptane, etc., and more specifically, p-xylene. The surface of the anode current collector coated with the anode slurry may be a single surface of the anode current collector or two surfaces of the anode current collector. The solid content of the anode slurry may be 40% by weight to 80% by weight. The viscosity of the anode slurry at room temperature can be adjusted to 5,000 mPa·s to 25,000 mPa·s. When coating the anode slurry, the coating unit area density on a dry weight basis (excluding solvent) is 15 mg / cm³. 2 Up to 35 mg / cm² 2 It can be. The compressive density of the anode film sheet is 3.0 g / cm³. 3 Up to 3.6 g / cm² 3 It may be, and optionally 3.3 g / cm³ 3 Up to 3.5 g / cm² 3 am.

[0293] As used in this application, "compressive density" has the meaning known in the art and is one of the reference indicators of the energy density of a material. In this application, unless otherwise specified, the compressive density of an electrode layer refers to the ratio of the mass of the electrode active material layer to its volume. The compressive density of an anode layer, anode sheet, anode film sheet, or anode film is the ratio of the mass to the volume of the anode active material layer, and the compressive density of a cathode layer, cathode sheet, cathode film sheet, or cathode film is the ratio of the mass to the volume of the cathode active material layer.

[0294] In another aspect of the present application, an anode film sheet is provided, comprising an anode current collector and an anode active material layer located on at least one side of the anode current collector, wherein the anode active material layer is the anode active material described in the second aspect of the present application.

[0295] This anode film sheet can be used directly as an anode sheet for assembling solid-state batteries, but is not limited thereto.

[0296] In a fourth aspect of the present application, a solid electrolyte membrane comprising the solid battery material described in the first aspect of the present application is provided, wherein the coated particles are coated electrolyte particles.

[0297] Non-limitingly, the solid electrolyte membrane may be an independent solid electrolyte membrane sheet and further used to assemble a solid-state battery; the solid electrolyte membrane may also be a solid electrolyte membrane layer existing within a composite structure.

[0298] This solid electrolyte membrane comprises coated electrolyte particles, and an oxygen storage layer installed on the surface of the coated electrolyte particles can reduce or isolate the decomposition of the sulfide electrolyte by oxygen in the air, and can also reduce or separate direct contact between the sulfide electrolyte and moisture in the air, thereby suppressing the decomposition of the sulfide electrolyte and the generation of hydrogen sulfide gas. This can improve the chemical stability of the sulfide electrolyte and the stability of the ion conductivity of the solid electrolyte membrane during the battery manufacturing process, promote stable operation of the solid battery, and is advantageous for improving the discharge capacity and cycle performance of the sulfide solid battery.

[0299] In some embodiments, the solid electrolyte membrane (10) is a solid electrolyte membrane (10a) comprising coated electrolyte particles (810), and reference may be made to FIG. 9.

[0300] A solid electrolyte membrane can be manufactured 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 comprising coated electrolyte particles can be pressed into a membrane, and additionally, the coated electrolyte particles can be pressed into a membrane. That is, the solid electrolyte membrane may comprise coated electrolyte particles and may be composed of coated electrolyte particles.

[0301] In the fifth aspect of the present application, a solid-state battery comprising the solid-state battery material described in the first aspect of the present application is provided.

[0302] In some embodiments, a solid-state battery comprising an anode layer, a solid electrolyte layer, and a cathode layer is provided;

[0303] Here, the solid-state battery is

[0304] The anode layer comprises an anode active material layer as described in the second embodiment of the present application;

[0305] The anode layer comprises an anode film as described in the third embodiment of the present application;

[0306] The solid electrolyte layer satisfies one or more of the features such as including a solid electrolyte membrane as described in the fourth aspect of the present application.

[0307] In some embodiments, a solid-state battery comprising an anode layer, a solid electrolyte layer, and a cathode layer is provided;

[0308] The solid-state battery comprises one or more solid-state battery materials as described in the first embodiment of the present application;

[0309] When the coated particles include coated anode active particles, the coated anode active particles are located in the anode layer;

[0310] When the coated particles include coated electrolyte particles, the coated electrolyte particles are located in at least one of the anode layer and the solid electrolyte layer.

[0311] In some embodiments, a solid-state battery is provided comprising an anode layer, a solid electrolyte layer, and a cathode layer; the anode layer comprises an anode active material layer, and the anode active material layer comprises anode active particles and anode electrolyte particles;

[0312] At least one of the solid electrolyte layer and the anode electrolyte particles comprises a sulfide electrolyte;

[0313] The solid-state battery comprises one or more solid-state battery materials as described in the first embodiment of the present application;

[0314] Solid-state batteries

[0315] (ta1) At least some of the anode electrolyte particles comprise a sulfide electrolyte (i.e., at least some of the anode electrolyte particles are sulfide-based electrolytes), and the anode active material layer comprises at least one of the coated anode active particles and the coated electrolyte particles; and

[0316] (ta2) The solid electrolyte layer satisfies at least one of the following characteristics, such as including coated electrolyte particles.

[0317] In some embodiments, the anode electrolyte particles are sulfide-based electrolytes, and the anode active material layer comprises at least one of the coated anode active particles and the coated electrolyte particles.

[0318] In some embodiments, the solid-state battery

[0319] The solid electrolyte layer and the anode electrolyte particles both contain a sulfide electrolyte, the sulfide electrolyte contained in the anode electrolyte particles is designated as the first sulfide electrolyte, the sulfide electrolyte contained in the solid electrolyte layer is designated as the second sulfide electrolyte, and the first sulfide electrolyte and the second sulfide electrolyte may be the same or different;

[0320] The anode electrolyte particles comprise a sulfide electrolyte, and at least one of the anode active particles and anode electrolyte particles satisfies one or more of the characteristics such as comprising the aforementioned coated particles.

[0321] In some embodiments, the anode electrolyte particles comprise a sulfide electrolyte, and at least one of the anode active particles and the anode electrolyte particles is the aforementioned coated particle.

[0322] In some embodiments, the anode electrolyte particles comprise a sulfide electrolyte, and the anode active particles comprise coated anode active particles, and furthermore, may be coated anode active particles.

[0323] In some embodiments, the anode electrolyte particles comprise a sulfide electrolyte, and the anode electrolyte particles comprise coated electrolyte particles, and furthermore, may be coated electrolyte particles.

[0324] In some embodiments, the anode electrolyte particles comprise a sulfide electrolyte, the anode active particles comprise coated anode active particles, and the anode electrolyte particles comprise coated electrolyte particles; optionally, the anode active particles are coated anode active particles and the anode electrolyte particles are coated electrolyte particles.

[0325] As described above, in the case of a solid-state battery (sulfide solid-state battery) in which the aforementioned solid-state battery material is installed in at least one of the anode layer and the solid electrolyte layer, when at least one of the anode active particles or coated electrolyte particles is used in the anode layer, when electrolyte particles are used in the solid electrolyte layer, or when the aforementioned solid-state battery material is used in both the anode layer and the solid electrolyte layer, it is advantageous to improve the discharge capacity and cycle performance of the solid-state battery.

[0326] In some embodiments, the solid electrolyte membrane (10) for manufacturing a solid battery is a solid electrolyte membrane (10b) comprising a sulfide-based electrolyte (910) without an oxygen storage layer, and reference can be made to FIG. 10.

[0327] In some embodiments, the solid electrolyte layer (100) is a solid electrolyte layer (100a) containing coated electrolyte particles (810), and reference can be made to FIG. 11.

[0328] In some embodiments, the solid electrolyte layer (100) is a solid electrolyte layer (100b) comprising a sulfide-based electrolyte (910) without an oxygen storage layer, and reference can be made to FIG. 12.

[0329] In the sixth aspect of the present application, an electric device comprising a solid-state battery as described in the fourth aspect of the present application is provided.

[0330] In the seventh aspect of the present application, the application of the solid battery material described in the first aspect of the present application, or the positive active material layer described in the second aspect of the present application, or the positive film described in the third aspect of the present application, or the solid electrolyte film described in the fourth aspect of the present application is provided in the manufacture of a solid battery.

[0331] In some embodiments of each aspect of the present application, the solid-state battery may be a sulfide solid-state battery. For the definition of a sulfide solid-state battery, refer to the foregoing.

[0332] In some embodiments of each aspect of the present application, the solid-state battery may be a sulfide all-solid-state battery. For the definition of a sulfide all-solid-state battery, refer to the foregoing.

[0333] Unless otherwise specified, the electrochemical performance of the battery related in this application generally includes overall performance in terms of at least discharge capacity and cycle performance.

[0334] A solid-state battery includes at least one solid-state battery cell. The solid-state battery may include one or more solid-state battery cells.

[0335] In this application, unless otherwise specified, "solid-state battery cell" refers to a basic unit capable of implementing the interconversion of chemical energy and electrical energy, and the constituent member is a solid. In some embodiments, the solid-state battery cell may be an all-solid-state battery cell.

[0336] Non-limitingly, 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 charging and discharging process of the battery, active ions are reciprocally inserted into and removed from the positive electrode layer and the negative electrode layer. The solid electrolyte layer serves as an ion conductor between the positive electrode layer and the negative electrode layer, and may also serve to separate the positive electrode layer and the negative electrode layer to prevent short circuits between them.

[0337] Unless otherwise specified, the positive layer in a solid-state battery comprises the positive film described in the first embodiment of the present application. It may be composed solely of the positive film described in the first embodiment of the present application, or the positive layer may be a combination of the positive film described in the first embodiment of the present application and another film suitable for the positive.

[0338] The following is a partial description of the solid electrolyte layer.

[0339] The solid electrolyte layer acts as an ion conductor between the anode and cathode layers, and can also serve to separate the anode and cathode layers to prevent short circuits between them.

[0340] The solid electrolyte layer can be understood to include a solid electrolyte. The solid electrolyte in the solid electrolyte layer may be a solid electrolyte known in the art that can be used in a solid-state battery.

[0341] The types of solid electrolytes present in different film layers of a solid-state battery may be the same or different. For example, the positive electrolyte particles and the solid electrolyte in the solid electrolyte layer may be the same or different.

[0342] As a non-limiting example, the anode electrolyte particles and the solid electrolyte in the solid electrolyte layer may each independently comprise one or more of the following materials: sulfide-type solid electrolytes, halide-type solid electrolytes, oxide-type solid electrolytes, polymer-type solid electrolytes, etc. The type of sulfide-type solid electrolyte in the solid electrolyte layer may be the same as or different from the sulfide-type solid electrolyte in the anode layer (e.g., the anode film described above). Taking the sulfide-type solid electrolyte as an example, the sulfide-type solid electrolyte refers to a solid electrolyte containing a sulfide electrolyte component; that is, the sulfide-type solid electrolyte is a type of sulfide-based electrolyte.

[0343] As another non-limiting example, the anode electrolyte particles and the solid electrolyte in the solid electrolyte layer may each independently comprise, but are not limited to, one or more of oxide-type solid electrolytes, sulfide-type solid electrolytes, and halide-type solid electrolytes. In some embodiments thereof, the anode electrolyte particles and the solid electrolyte in the solid electrolyte layer may each independently comprise, but are not limited to, one or more of argyrodite-type sulfide electrolytes and halide electrolytes. Here, non-limiting examples of oxide-type solid electrolytes include LISICON-type oxide electrolytes (e.g., γ-Li3PO4, etc.) and NASICON-type oxide electrolytes (e.g., Li1 + x Al x Ge2 -x (PO4)3, Li1 + x Al x Ti2 -x (PO4)3, etc., 0≤x≤1), Garnet type (e.g., Li7La3Zr2O12, etc.), Perovskite type oxide electrolytes (e.g., Li 3x La2 / 3- x It may include one or more of TiO3, etc. (0≤x≤0.5). Non-limiting examples of sulfide-type solid electrolytes include Li 10GeP2S 12 , Li2S-P2S5, argyrodite type (e.g., Li6PS5Cl, Li5 . 5PS5 . 5Cl1 .5 It may include one or more of the following. Non-limiting examples of halogen-type solid electrolytes may include one or more of Li3InCl6, Li3YCl6, Li3ScCl6, Li3ErCl6, Li2ZrCl6, etc.

[0344] In some embodiments, the solid electrolyte layer may be manufactured by compressing a solid electrolyte material into a solid electrolyte membrane sheet.

[0345] In some embodiments, the thickness of the solid electrolyte layer may be 0.1 μm to 1000 μm, and optionally 10 μm to 100 μm, 100 μm to 800 μm, 500 μm to 800 μm, etc.

[0346] The following is a partial description of the cathode layer.

[0347] The cathode layer may be provided as a cathode sheet or a cathode film sheet of the present art that can be used in a solid-state battery, and a cathode film layer may be formed by directly pressing the constituent material of the cathode layer onto one side of the solid electrolyte layer. The cathode film sheet may be combined with other films suitable for the cathode to form a cathode sheet or a cathode layer.

[0348] The cathode layer can be manufactured using a dry or wet method. For example, a film can be formed using a dry pressing process. Additionally, a film can be formed through a wet coating process, for example.

[0349] The cathode layer includes a cathode active material layer, the cathode active material layer includes cathode active particles, and the cathode active particles contain a cathode active material.

[0350] Non-limitingly, the weight percentage of cathodic active particles or cathodic active material in the cathodic active material layer may be ≥80 weight%, and furthermore, ≥90 weight%.

[0351] In some embodiments, the cathode active particle or cathode active material comprises a lithium indium alloy (InLi alloy).

[0352] In some embodiments, the cathode layer is an InLi alloy film.

[0353] In some embodiments, the negative electrode active material may be a negative electrode active material that can be used in solid-state batteries known in the art. As a non-limiting example, the negative electrode active material may include one or more of the following materials: solid silicon, solid tin, silicon-carbon negative (silicon-carbon composite material), silicon oxide, graphite, and metallic lithium. However, the present application is not limited to these materials or substances, and other conventional materials that can be used as battery negative electrode active materials may also be used. Such negative electrode active materials may be used alone or in combination of two or more.

[0354] In some embodiments, the cathode sheet or cathode film sheet may comprise a cathode current collector and a cathode active material layer installed on at least one surface of the cathode current collector, and the cathode active material layer comprises a cathode active material. As a non-limiting example, the cathode current collector has two surfaces opposite each other in its own thickness direction, and the cathode active material is installed on either or both of the two opposite surfaces of the cathode current collector. In some embodiments, the cathode current collector may use a metal foil or a composite current collector. For example, copper foil may be used as the metal foil. In the cathode current collector, the composite current collector may comprise a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. In the cathode current collector, the composite current collector may be formed by forming a metal material on the polymer material substrate. In the cathode current collector, non-limiting examples of this metal material may include one or more of copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver, and silver alloy. In the cathode current collector, non-limiting examples of this polymer material substrate may include one or more of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.

[0355] In some embodiments, the cathode active material layer optionally comprises a cathode conductive agent. Non-limitingly, the cathode conductive agent may comprise one or more of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon quantum dots, carbon nanotubes, graphene, and carbon nanofibers. Non-limitingly, in the cathode active material layer, the weight percentage of the cathode conductive agent may be 0 to 15 weight%, more optionally 0 to 10 weight%, and even more optionally 0 to 5 weight%.

[0356] In some embodiments, the cathode active material layer optionally comprises an adhesive (referred to as cathode adhesive). As a non-limiting example, the cathode adhesive may comprise one or more of styrene-butadiene rubber (SBR), polyacrylic acid type (PAA type), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS). Non-limitingly, the weight percentage of the cathode adhesive in the cathode active material layer may be 0 to 10 weight%, more specifically 0 to 5 weight%, more specifically 1 to 5 weight%, and more specifically 1 to 3 weight%.

[0357] In some embodiments, the cathode active material layer optionally comprises other auxiliary agents such as a thickener (e.g., sodium carboxymethylcellulose (CMC-Na)). The weight percentage of other auxiliary agents in the cathode active material layer may be 0 to 15 weight%, more optionally 0 to 10 weight%, even more optionally 0 to 5 weight%, even more optionally 0 to 3 weight%, and even more optionally 0 to 2 weight%.

[0358] In some embodiments, a cathode sheet or a cathode film sheet may be manufactured in the following manner: a cathode slurry is formed by dispersing each of the above-described components used in manufacturing the cathode sheet or cathode film sheet, e.g., cathode active particles, cathode conductive agents, adhesives (i.e., cathode adhesives), and any other components in a solvent (non-limiting examples of solvents include, e.g., N-methylpyrrolidone (NMP)). Additionally, the cathode slurry may be coated onto at least one surface of a cathode current collector and a cathode sheet or a cathode film sheet may be obtained through processes such as drying and cold pressing. Cold pressing may be performed using a cold rolling mill. The surface of the cathode current collector coated with the cathode slurry may be a single surface of the cathode current collector or two surfaces of the cathode current collector. The solid content of the cathode slurry may be 30% by weight to 70% by weight, and optionally 40% by weight to 60% by weight. The viscosity of the cathode slurry at room temperature can be adjusted to 2,000 mPa·s to 10,000 mPa·s, and optionally to 3,000 mPa·s to 10,000 mPa·s. When coating the cathode slurry, the coating unit area density on a dry weight basis (excluding solvent) is 75 g / m². 2 Up to 220g / m² 2 It may be. The compressed density of the cathode sheet or cathode film sheet is 1.0 g / cm³ 3 Up to 2.0 g / cm² 3 It may be, and optionally 1.0 g / cm³ 3 Up to 1.8 g / cm² 3 am.

[0359] A solid cell can be manufactured by sequentially stacking an anode sheet, a solid electrolyte membrane sheet, and a cathode sheet, placing the solid electrolyte membrane sheet between the anode sheet and the cathode sheet, and hot rolling.

[0360] A solid cell can be manufactured by sequentially stacking an anode film sheet, a solid electrolyte film sheet, and a cathode film sheet, placing the solid electrolyte film sheet between the anode film sheet and the cathode film sheet, and hot rolling.

[0361] In some embodiments, the solid battery cell (5) includes a solid cell (52).

[0362] In some embodiments, the solid cell is an all-solid cell.

[0363] In some embodiments, the solid cell (52) (which may be an all-solid cell) comprises a sequentially stacked anode layer (200), a solid electrolyte layer (100), and a cathode layer (300), one example of which may be referenced in FIG. 15. Unless otherwise specified, the anode layer (200) comprises an anode film (20).

[0364] In some embodiments, the solid cell (52) comprises a positive electrode layer (200), a solid electrolyte layer (100), and a negative electrode layer (300) stacked sequentially, wherein the positive electrode layer (200) comprises a positive electrode film (20), the positive electrode film (20) comprises a positive electrode current collector (210) and a positive electrode active material layer (220) located on both sides of the positive electrode current collector, and the positive electrode active material layer (220) is installed between the positive electrode current collector (210) and the solid electrolyte layer (100). One example thereof may be referenced in FIG. 16.

[0365] In some embodiments, the solid-state battery may include an outer casing. This outer casing may be used to seal and package the solid-state cell described above.

[0366] In some embodiments, the outer casing of the solid-state battery may be a hard case, such as a hard plastic case, an aluminum case, a steel case, etc. The outer casing of the solid-state battery may also be a soft pack, such as a pouch-type soft pack. The material of the soft pack may be plastic, and additionally, non-limiting examples of the plastic may include one or more of polypropylene, polybutylene terephthalate, and polybutylene succinate.

[0367] The present application has no particular limitation on the shape of the solid battery cell and may be cylindrical, square, or any other shape. For example, FIG. 17 is a solid battery cell (5) with a square structure as an example.

[0368] In some embodiments thereof, referring to FIG. 18, the outer member may include a case (51) and a cover plate (53). Here, the case (51) may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate surround to form a receiving chamber. The case (51) has an opening communicating with the receiving chamber, and the cover plate (53) may be installed as a cover over the opening to close the receiving chamber. A solid cell (52) is sealed and packaged within the receiving chamber. The number of solid cells (52) included in the solid battery cell (5) may be one or more, and a person skilled in the art may select according to actual demand.

[0369] The solid-state battery can be a battery module (4) or a battery pack (1).

[0370] The battery module includes at least one solid-state battery cell. The number of solid-state battery cells included in the battery module may be one or more, and an appropriate number can be selected according to the application and capacity of the battery module for those with ordinary knowledge in the art.

[0371] FIG. 19 is a battery module (4) as an example. Referring to FIG. 19, in the battery module (4), a plurality of solid-state battery cells (5) may be installed in a sequential arrangement along the length direction of the battery module (4). Of course, they may also be arranged in any other arbitrary way. These plurality of solid-state battery cells (5) may be further secured through fastening members.

[0372] Optionally, the battery module (4) may include a housing having a receiving space, and a plurality of solid battery cells (5) are received in this receiving space.

[0373] In some embodiments thereof, the above-described battery module may be assembled into a battery pack, and the number of battery modules included in the battery pack may be one or more, and a person with ordinary knowledge in the art may select an appropriate number according to the application and capacity of the battery pack.

[0374] FIGS. 20 and 21 are a battery pack (1) as an example. Referring to FIGS. 20 and 21, the battery pack (1) may include a battery box and a plurality of battery modules (4) installed in the battery box. The battery box includes an upper box body (2) and a lower box body (3), and the upper box body (2) may be covered and installed on the lower box body (3) to form a sealed space for accommodating the battery modules (4). The plurality of battery modules (4) may be arranged in any manner within the battery box.

[0375] In some of the embodiments thereof, the electric device includes a solid-state battery according to any embodiment provided in the present application.

[0376] Without limitation, solid-state batteries may be used as power sources for electric devices and as energy storage units for electric devices. Electric devices may include, but are not limited to, mobile devices, electric vehicles, electric trains, ships and satellites, energy storage systems, etc. Here, mobile devices may be, for example, mobile phones, laptop computers, etc., and electric vehicles may be, for example, pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, electric motorcycles, power tools, etc., but are not limited thereto. These electric devices may also be applied to fields such as military equipment and aerospace, and may be applied to energy storage power systems such as hydroelectric, thermal, wind, and solar power plants.

[0377] As an electrical device, a solid-state battery can be selected according to its usage demand.

[0378] FIG. 22 is an electric device (6) as an example. This electric device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle. To meet the requirements of this electric device for high power output and high energy density of solid-state batteries, a battery pack or battery module may be used.

[0379] Another example of such a device could be a mobile phone, tablet, or laptop computer. These devices generally require lightweight design and can use solid-state batteries as a power source.

[0380] Some embodiments of the present application are described below. The embodiments described below are illustrative and are intended only for the interpretation of the present application and should not be understood as a limitation thereof. Where no description or condition is specified in an embodiment, it is performed in accordance with the description above, in accordance with the description or condition described in literature of the art, or in accordance with the product description. The reagents or equipment used are not labeled with the manufacturer and are all ordinary products available on the market or synthesized in the ordinary manner using products available on the market.

[0381] Unless otherwise specified, in each of the following examples and comparative examples, raw materials having the same chemical formula are derived from the same synthesis batch or raw materials of the same catalog number, or are manufactured according to the same stoichiometric ratio and the same method.

[0382] In the following examples, room temperature refers to 20°C to 30°C.

[0383] D v 50 tests:

[0384] In each of the following examples and comparative examples, D of the anode active particles, anode electrolyte particles, and oxygen storage particles v 50 can be tested and verified using the following method: Instrument model: Malvern 2000 (MasterSizer 2000) laser particle size analyzer; Reference standard procedure: GB / T19077-2016 / ISO 13320:2009; Test procedure: Take an appropriate amount of the sample to be tested (ensure light shielding with a sample concentration of 8% to 12% (w / v)), add 20 mL of solvent (e.g., p-xylene or deionized water), and simultaneously sonicate (53KHz / 120W) for 5 minutes to ensure the sample is completely dispersed, and then measure the sample according to the GB / T19077-2016 / ISO 13320:2009 standard.

[0385] Unless otherwise specified, D of the anode-active particles and electrolyte particles related to each of the following examples v The record value of 50 follows the "rounding" coefficient rule.

[0386] The transmission electron microscope (TEM) instrument model is FEI / Talos, F200X, and the test acceleration voltage is 200 kV. This instrument integrates high-resolution scanning / transmission electron microscopy (STEM) and TEM imaging capabilities, energy dispersive X-ray spectroscopy (EDS) signal detection capabilities, and component mapping-based three-dimensional chemical characterization capabilities.

[0387] XRD test device and parameters: D8 Advance Da Vinci X, Cu Kα1, 2θ scan range 20° to 110°, scan speed 5° / min.

[0388] In each of the following examples, unless otherwise specified, when a target coated particle is obtained by coating a particle body using an oxygen storage material, "amount of coating of oxygen storage material" or "amount of coating of oxygen storage layer" refers to the weight percentage of the oxygen storage material in the target coated particle.

[0389] In each of the following examples, YBaCo4O7(YBCO) is a yttrium barium cobalt oxide type oxygen storage material, and La0 . 8Sr0 . 2COO3 is a perovskite-type oxygen storage material, and La2O2SO4 and CeO .6 Zr 0.3 Al 0.1 O 1.95 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, and Li1 . 2Mn0 . 48 Ni0 . 16 Co0 . 16 O2 is a lithium-rich manganese-based lithium transition metal oxide.

[0390] In each of the following examples and comparative examples, unless otherwise specified, the steps involving the sulfide-based electrolyte material are performed in an argon atmosphere.

[0391] In each of the following embodiments and each embodiment, it must be stated that a sulfide all-solid-state battery is used as a non-limiting example of an all-solid-state battery.

[0392] a. Preparation Example

[0393] (a) Use of coated positively active particles

[0394] Examples 1. Coated positive active particles, a positive film, a positive layer, and a corresponding solid-state battery (sulfide solid-state battery) were prepared.

[0395] (1) 2 wt% of YBaCO4O7 (YBCO, oxygen storage material) with LiNiO . 8Co0 . 1Mn0 . 1O2 (NCM811 or NCM 811 Coated positively active particles were prepared by coating a positively active body (used as the positively active body).

[0396] Y2O3, BaCO3, and Co3O4 were weighed according to the stoichiometric ratio of the oxygen storage material and mixed, stirred, and ball-milled in an organic solvent (ethanol) to uniformly disperse the raw materials. The ball-milled raw materials were then dried in an air blast drying oven at 80°C, heat-treated at 1000°C for 12 hours in an air atmosphere, and the sintered sample was ground and then heat-treated at 1100°C for 24 hours to obtain the YBCO oxygen storage material.

[0397] Refer to Figure 23 for the XRD pattern of the YBCO oxygen storage material manufactured in this example.

[0398] The obtained YBCO oxygen storage material was ground into oxygen storage particles having nano-sized dimensions (1 nm to 50 nm) using a sand mill, and then the YBCO oxygen storage particles having nano-sized dimensions were uniformly mixed with NCM811 using a dry coating device with a coating amount of 2 wt% oxygen storage material. The obtained material was heat-treated at 450°C for 5 hours in an argon atmosphere to obtain coated positive active particles having an NCM811 positive material structure coated with 2 wt% YBCO, which may also be labeled as "2 wt% YBaCO4O7-coated NCM811 positive active particles," and can be used as a backup solid-state battery material.

[0399] According to transmission electron microscopy (TEM) detection and analysis, it can be observed that YBCO is better coated on the surface of the anode material NCM811, and the thickness of the surface coating layer (i.e., oxygen storage layer) is about 2 nm. Refer to Fig. 24.

[0400] (2) A positive film sheet was manufactured (used as a positive film, a positive film for solid-state batteries).

[0401] Under an argon atmosphere, 2 wt% YBaCo4O7-coated NCM811 anode active particles (D v 50 is 4μm), Li6PS5Cl sulfide electrolyte (D v 50 (1 μm), conductive agent VGCF (vapor-grown carbon fiber), and adhesive polytetrafluoroethylene (PTFE) were each weighed in a weight ratio of 85:13:1:1 and uniformly mixed in a dual planetary mixer. Then, the uniformly mixed powder was heated and pressurized in an internal mixer to form a lump-shaped material, and then hot-rolled at 80°C to produce a self-standing anode sheet. Finally, an anode film sheet was obtained by hot-rolling and combining it with aluminum foil, which is an anode current collector.

[0402] (3) A solid electrolyte membrane sheet (solid electrolyte membrane) was manufactured and an all-solid-state battery was assembled.

[0403] 100 mg of sulfide electrolyte LPSCl was weighed in an argon atmosphere, added to a battery mold, and pressurized to obtain a solid electrolyte membrane sheet. Then, an anode membrane sheet was placed on one side of the solid electrolyte membrane sheet, and an InLi alloy was laminated as a cathode layer on the other side to assemble an all-solid-state battery. At this time, the solid electrolyte membrane sheet was used as the solid electrolyte layer, and the anode membrane sheet was used as the anode layer.

[0404] The test window of the battery is 2.8 to 4.3V vs Li.

[0405] Examples 2. Oxygen storage material in coated anodic active particles Coating amount Changed

[0406] Coated positive active material, positive film, and all-solid-state battery were prepared using a method basically identical to that of Example 1, with the difference being that the coating amount of the YBCO coating layer was 1 wt% and the thickness of the oxygen storage layer was approximately 1 nm. The remaining steps were the same as in Example 1. Refer to Table 1.

[0407] Examples 3. Oxygen storage material in coated anodic active particles Coating amount Changed

[0408] Coated positive active material, positive film, and all-solid-state battery were prepared using a method basically identical to that of Example 1, with the difference being that the coating amount of the YBCO coating layer was 3 wt% and the thickness of the oxygen storage layer was about 3 nm to 4 nm. The remaining steps were the same as in Example 1. Refer to Table 1.

[0409] Examples 4. Types of oxygen storage materials in coated anodic active particles and Coating amount Changed

[0410] Coated positive active material, positive film, and all-solid-state battery were prepared using a method basically identical to that of Example 1, the difference being that the coated positive active particles are different and 1 wt% LaO. 8Sr0 . LiNiO with 2CoO3 . 8Co0 . 1Mn0 . It is said that anode active particles obtained by coating 1O2 (NCM811, anode active body) were used. Refer to Table 1.

[0411] La(NO3)3·6H2O, Co(NO3)2·6H2O, Sr(NO3)2, and hexadecyltrimethylammonium bromide were added to deionized water in stoichiometric ratios and stirred, then the pH was adjusted to 9 using ammonia, and after the raw materials were sufficiently dissolved, the NCM811 cathode active material (D v 50 (4 μm) is added, heated and stirred in an oil bath at 80°C until the solvent completely evaporates, and the collected powder is heated at 500°C for 5 hours to obtain 1 wt% LaO . 8Sr0 . Coated anode active particles having a 2CoO3-coated NCM811 structure were obtained, and "1 wt% La0 . 8Sr0 . It can be referred to as "2CoO3-coated NCM811".

[0412] According to TEM test results, the thickness of the surface coating layer (i.e., oxygen storage layer) is about 2 nm.

[0413] Examples 5. Types of oxygen storage materials in coated anodic active particles Changed

[0414] Coated positive active material, positive film, and all-solid-state battery were prepared using a method basically identical to that of Example 1, the difference being that the coated positive active particles are different and LiNiO is used with 2 wt% La2O2SO4. . 8Co0 . 1Mn0 . It is said that anode active particles obtained by coating 1O2 (NCM811, anode active body) were used. Refer to Table 1.

[0415] La(NO3)3·6H2O and sodium dodecylsulfonate CH3(CH2) 10 CH2SO3Na is added to deionized water according to stoichiometric ratios and stirred, and ammonia is added to adjust the pH to 9. After the raw material is sufficiently dissolved, LiNiO . 8Co0 . 1Mn0 . 1O2 anode active material (D v 50 (4 μm) was added, heated and stirred in an oil bath at 80°C until the solvent was completely evaporated, and the collected powder was heated at 550°C for 5 hours to obtain coated anode active particles having a 2 wt% La2O2SO4-coated NCM811 structure.

[0416] According to TEM test results, the thickness of the surface coating layer (i.e., oxygen storage layer) is about 2 nm.

[0417] Examples 6 to 9. Oxygen storage material in coated anodic active particles Coating amount Changed

[0418] Coated positive active material, positive film, and all-solid-state battery were prepared using a method basically identical to that of Example 1, with the difference being that the coating amount of the oxygen storage material was different, and can be seen in Table 1.

[0419] Examples 10 to 11. Types of anode active materials in coated anode active particles Changed

[0420] Coated positive active materials, positive films, and all-solid-state batteries were prepared using a method essentially identical to that of Example 1, with the difference being the type of positive active material among the coated positive active particles; LiCoO2 was used in Example 10, while LiCoO2 was used in Example 11. 1.2 Mn 0.48 Ni 0.16 Co 0.16 This means that O2 was used, and you can refer to Table 1.

[0421] Examples 12 to 13. of coated anodic active particles D v 50 Changed.

[0422] A coated positive active material, a positive film, and an all-solid-state battery were prepared using a method basically identical to that of Example 1, with the difference being the use of positive active bodies with different particle sizes D v 50 different coated anode active particles were prepared. Refer to Table 1.

[0423] Examples 14. Anode In the active material layer The capacity of the coated anode active particles was changed.

[0424] Coated positive active material, positive film, and all-solid-state battery were prepared using a method basically identical to that of Example 1, with the difference being that the capacity of the coated positive active particles in the positive active material layer was different, and in the case where the total weight ratio of the positive active particles in the positive active material layer was the same, 15 wt% of NCM811 was used instead of the coated positive active particles of Example 1, that is, a mixture of coated positive active particles (2 wt% YBaCo4O7-coated NCM811 positive active particles) and positive active particles without an oxygen storage layer (NCM811) was used as the positive active particles; in the step of preparing the positive film sheet, the weight ratio of the coated positive active particles, positive active particles without an oxygen storage layer, conductive agent VGCF, and adhesive was 70:15:13:1:1. Refer to Table 1.

[0425] Comparative example 1. The positively active particles are oxygen storage layer There is no coating layer including what is missing.

[0426] A positive electrode film and an all-solid-state battery were prepared using a method basically identical to that of Example 1, the difference being that the positive electrode active particles used are NCM811 positive electrode active materials without any surface coating. That is, in step (2), 2 wt% YBaCo4O7-coated NCM811 negative electrode active particles (D v50 is an NCM811 cathode material without any surface coating (D) instead of 4 μm) v 50 used (approximately 4 μm).

[0427] Comparative example 2 to 3. The anode active particles are provided with a coating layer, but oxygen storage layer None; instead of oxygen storage materials Non-oxygen It was coated using storage materials.

[0428] Comparative Example 2 prepared a coated positive active material, a positive film, and an all-solid-state battery using basically the same method as Example 1, but the difference is that the positive active particles used are NCM811 positive active materials coated with Li2ZrO3, and the thickness of the Li2ZrO3 coating layer is about 2 nm.

[0429] Comparative Example 3 prepared a coated positive active material, a positive film, and an all-solid-state battery using basically the same method as Example 1, but the difference is that the positive active particles used are NCM811 positive active materials coated with LiNbO3, and the thickness of the LiNbO3 coating layer is about 2 nm.

[0430] Comparative example 4. Anodic activity In the case of particles , oxygen in coating form Storage layer Instead, oxygen storage materials were introduced using a physical mixing method.

[0431] Comparative Example 4 prepared a coated positive active material, a positive film, and an all-solid-state battery using basically the same method as Example 1, but the difference is that the step of preparing the coated positive active particles was omitted and the composition of the positive film sheet was different.

[0432] In Comparative Example 4, 0.2g of YBaCo4O7(D v 50 (approx. 200 nm) and 10 g of NCM811 material were ground and mixed in a mortar to obtain NCM811 mixed and doped with an oxygen storage material, and then the NCM811 mixed and doped with the oxygen storage material was mixed with a Li6PS5Cl sulfide electrolyte (D v50 (1 μm), conductive agent VGCF (vapor-grown carbon fiber), and adhesive polytetrafluoroethylene (PTFE) were mixed in a weight ratio of 85:13:1:1 and uniformly mixed in a dual planetary mixer. Then, the uniformly mixed powder was heated and pressurized in an internal mixer to form a lump-shaped material, and then hot-rolled at 80°C to produce a self-standing anode sheet. Finally, an anode film sheet was obtained by hot-rolling and combining it with aluminum foil, which is an anode current collector.

[0433] Table 1. Relevant parameters of coated anodic active particles

[0434] turn Oxygen storage layer of coated positively active particles Types of positive active materials in the positive active body D of coated positively active particles v 50 Chemical formula of oxygen storage material Weight ratio of coated particles of oxygen storage material Oxygen storage layer thickness Example 1 YBaCo4O7 2 wt% Approximately 2nm NCM811 Approximately 4 μm Example 2 YBaCo4O7 1 wt% Approximately 1 nm NCM811 Approximately 4 μm Example 3 YBaCo4O7 3 wt% About 3 nm to 4 nm NCM811 Approximately 4 μm Example 4 La0 . 8Sr0 . 2CoO3 1 wt% Approximately 2nm NCM811 Approximately 4 μm Example 5 La2O2SO4 2 wt% Approximately 2nm NCM811 Approximately 4 μm Example 6 YBaCo4O7 0.5 wt% Approximately 0.5nm NCM811 Approximately 4 μm Example 7 YBaCo4O7 5 wt% Approximately 6nm NCM811 Approximately 4 μm Example 8 YBaCo4O7 0.1 wt% Approximately 0.1 nm NCM811 Approximately 4 μm Example 9 YBaCo4O7 10 wt% Approximately 12 nm NCM811 Approximately 4 μm Example 10 YBaCo4O7 2 wt% Approximately 2nm LiCoO2 Approximately 4 μm Example 11 YBaCo4O7 2 wt% Approximately 2nm Li 1.2 Mr 0.48 Ni 0.16 Co 0.16 O2 Approximately 4 μm Example 12 YBaCo4O7 2 wt% 2 wt% NCM811 Approximately 1 μm Example 13 YBaCo4O7 2 wt% 2 wt% NCM811 Approximately 10μm Example 14 YBaCo4O7 2 wt% Approximately 2nm NCM811 Approximately 4 μm

[0435] (b) Use of coated electrolyte particles

[0436] Examples X1. Coated electrolyte particles (2 wt% La2O2SO4-coated Li5 . 5PS4 . 5Cl1 .5 A sulfide electrolyte), a solid electrolyte membrane, and a corresponding all-solid-state battery were manufactured.

[0437] (1) Coated electrolyte particles were prepared.

[0438] La(NO3)3·6H2O, sodium dodecylsulfonate CH3(CH2) 10 A solution was prepared using CH2SO3Na, ammonia, and deionized water in a molar ratio of 2:1:30:60, placed in a 40°C constant temperature water bath and maintained for 1 hour, then the temperature was raised to 50°C and stirred continuously for 10 hours to adjust the pH of the solution to 9. Then, it was filtered by suction and washed until neutral, and finally, heat-treated at 550°C for 5 hours in an air atmosphere to obtain a crude La2O2SO4 product. The obtained crude La2O2SO4 product was further ground using a sand mill to obtain nano-sized oxygen storage particles (1 nm to 50 nm), which were used as a La2O2SO4 oxygen storage material for subsequent coating steps.

[0439] In a glove box protected by an argon atmosphere, 0.2 g of the previously synthesized nano La2O2SO4 oxygen storage material was weighed into a glass beaker, an appropriate amount of p-xylene solvent was added, and the mixture was stirred sufficiently to obtain a colloidal solution, and then Li5 . 5PS4 . 5Cl1 .5 Sulfide solid electrolyte (D v 10g of 50 (approx. 1μm) was added and stirred continuously for 3 hours, then placed in a vacuum oven and vacuum dried at 120°C for 10 hours to obtain coated electrolyte particles, and 2 wt% La2O2SO4-coated Li5 . 5PS4 . 5Cl1 .5 It can be described as a sulfide electrolyte.

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

[0441] (2) A positive film sheet was manufactured.

[0442] LiNi0 in an argon atmosphere . 8Co0 . 1Mn0 . 1O2(NCM811) positively active particles (D v 50 is 4μm), coated electrolyte particles (previously prepared 2 wt% La2O2SO4-coated Li5 . 5PS4 . 5Cl1 .5 A sulfide electrolyte), a conductive agent VGCF (vapor-growthed carbon fiber), and an adhesive polytetrafluoroethylene (PTFE) were each weighed in a weight ratio of 85:13:1:1 and uniformly mixed in a dual planetary mixer. Then, the uniformly mixed powder was heated and pressurized in an internal mixer to form a lump-shaped material, and then hot-rolled at 80°C to produce a self-standing anode sheet. Finally, an anode film sheet was obtained by hot-rolling and combining it with an aluminum foil, which is an anode current collector.

[0443] (3) Sulfide electrolyte Li5 in an argon atmosphere . 5PS4 . 5Cl1 . 5100 mg was weighed and added to a battery mold and pressurized to obtain a solid electrolyte membrane sheet, then a positive electrode membrane sheet was placed on one side of the solid electrolyte membrane sheet and an InLi alloy was laminated as a negative electrode layer on the other side to assemble an all-solid-state battery.

[0444] Examples X2. The coated electrolyte particles are 2 wt% YBaCO4O7-coated Li5 . 5PS4 . 5Cl1 .5 It is a sulfide electrolyte.

[0445] Anode film sheets and all-solid-state batteries were prepared using a method essentially identical to that of Example X1, the difference being that the coated electrolyte particles used in the preparation of the anode film sheets were different; the coated electrolyte particles used in this example were 2 wt% YBaCo4O7-coated Li 5.5 PS 4.5 Cl 1.5 It is a sulfide electrolyte.

[0446] (1) Y2O3, BaCO3, and Co3O4 were weighed according to stoichiometric ratios and mixed, stirred, and ball-milled in an organic solvent (ethanol) to uniformly disperse the raw materials. The ball-milled raw materials were then dried in an air blast drying oven at 80°C, heat-treated at 1000°C for 12 hours in an air atmosphere, and the sintered sample was ground and then heat-treated at 1100°C for 24 hours to obtain the desired YBaCO4O7 crude product. The obtained YBaCO4O7 crude product was further ground using a sand mill to obtain oxygen storage particles of nano-sized dimensions (1 nm to 50 nm), which were used as YBaCO4O7 oxygen storage materials for subsequent coating steps.

[0447] In a glove box protected by an argon atmosphere, 0.2 g of the previously synthesized nano YBaCO4O7 oxygen storage material was weighed into a glass beaker, an appropriate amount of p-xylene solvent was added, and the mixture was stirred sufficiently to obtain a colloidal solution, and then Li5 . 5PS4 . 5Cl1 .5 Sulfide solid electrolyte (D v 10g of 50 (approx. 1μm) was added and stirred continuously for 3 hours, then placed in a vacuum oven and vacuum dried at 120°C for 10 hours to obtain coated electrolyte particles, and 2 wt% YBaCO4O7-coated Li5 . 5PS4 . 5Cl1 .5 It can be described as a sulfide electrolyte.

[0448] According to the TEM test analysis results, the thickness of the obtained coating layer (oxygen storage layer) is about 2 nm.

[0449] Examples X3. The coated electrolyte particles contain 1 wt% La0 . 8Sr0 . 2CoO3-coated Li5 . 5PS4 . 5Cl1 .5 It is a sulfide electrolyte.

[0450] An anode film sheet and an all-solid-state battery were manufactured using a method essentially identical to that of Example X1, the difference being that the coated electrolyte particles used in the manufacture of the anode film sheet were different; the coated electrolyte particles used in this example were 1 wt% La0 . 8Sr0 . 2CoO3-coated Li 5.5 PS 4.5 Cl 1.5 It is a sulfide electrolyte.

[0451] (1) Weigh La(NO3)3·6H2O, Co(NO3)2·6H2O, and Sr(NO3)2 according to stoichiometric ratios and add them to deionized water, then La0 . 8Sr0 .A complex solution was prepared by adding urea such that the molar ratio of 2CoO3 to urea was 1:4. The solution was placed in an 80°C water bath and stirred continuously, after which ammonia was added dropwise to adjust the pH of the solution to 9. The obtained precipitate was filtered by suction and washed until neutral. The resulting powder was sintered at 700°C for 5 hours in an air atmosphere, and the sintered sample was ground and then sintered at 1050°C for 10 hours to obtain the desired La 0.8 Sr 0.2 CoO3 oxygen storage material was obtained. The obtained LaO . 8Sr0 . 2CoO3 was further ground using a sand mill to obtain nano-sized oxygen storage particles (1 nm to 50 nm), and Li5 for subsequent step coating was used. . 5PS4 . 5Cl1 .5 It was used as an oxygen storage material.

[0452] In a glove box protected by an argon atmosphere, the previously synthesized nano La0 . 8Sr0 . 0.1g of 2CoO3 oxygen storage material was weighed into a glass beaker, an appropriate amount of p-xylene solvent was added, and a colloidal solution was obtained by stirring sufficiently, and then Li5 . 5PS4 . 5Cl1 .5 Sulfide solid electrolyte (D v 10g of 50 (approx. 1μm) was added and stirred continuously for 3 hours, then placed in a vacuum oven and vacuum dried at 120°C for 10 hours to obtain coated electrolyte particles, with 1 wt% LaO . 8Sr0 . 2CoO3-coated Li5 . 5PS4 . 5Cl1 .5 It can be described as a sulfide electrolyte.

[0453] According to the TEM test analysis results, the thickness of the obtained coating layer (oxygen storage layer) is about 2 nm.

[0454] ExamplesX4. The coated electrolyte particles contain 1 wt% Ce0 . 6Zr0 . 3Al0 . 101 .95 -Coated Li 5.5 PS 4.5 Cl 1.5 It is a sulfide electrolyte.

[0455] Anode film sheets and all-solid-state batteries were manufactured using a method essentially identical to that of Example X1, the difference being that the coated electrolyte particles used in the manufacture of the anode film sheets were different; the coated electrolyte particles used in this example were 1 wt% Ce0 . 6Zr0 . 3Al0 . 101 .95 -Coated Li5 . 5PS4 . 5Cl1 .5 It is a sulfide electrolyte.

[0456] (1) Weigh cerium nitrate, zirconium nitrate, and aluminum nitrate according to stoichiometric ratios, add deionized water, and then Ce0 . 6Zr0 . 3Al0 . 101 .95 A complex solution was prepared by adding urea such that the molar ratio of urea to urea was 1:4. The solution was placed in an 80°C water bath and stirred continuously, after which ammonia was added dropwise to adjust the pH of the solution to 9. The obtained precipitate was filtered by suction and washed until neutral. The obtained powder was sintered at 500°C for 5 hours in an air atmosphere, and 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 Early products were obtained. The obtained Ce0 . 6Zr0 . 3Al0 . 101 .95The crude product was further ground using a sand mill to obtain nano-sized oxygen storage particles (1 nm to 50 nm), and Li5 for subsequent step coating. . 5PS4 . 5Cl1 .5 It was used as an oxygen storage material.

[0457] In a glove box protected by an argon atmosphere, the previously synthesized nano Ce 0.6 Zr 0.3 Al 0.1 O 1.95 0.1g of oxygen storage material was weighed into a glass beaker, an appropriate amount of p-xylene solvent was added, and a colloidal solution was obtained by stirring sufficiently, and then Li 5.5 PS 4.5 Cl 1.5 Sulfide solid electrolyte (D v 10g of 50 (approx. 1μm) was added and stirred continuously for 3 hours, then placed in a vacuum oven and vacuum dried at 120°C for 10 hours to obtain coated electrolyte particles, with 1 wt% CeO . 6Zr0 . 3Al0 . 101 .95 -Coated Li5 . 5PS4 . 5Cl1 .5 It can be described as a sulfide electrolyte.

[0458] According to the TEM test analysis results, the thickness of the obtained coating layer (oxygen storage layer) is about 2 nm.

[0459] Examples X5 to X8. Oxygen storage material in coated electrolyte particles Coating amount Changed

[0460] Coated electrolyte particles, anode film sheets, and all-solid-state batteries were prepared using a method basically identical to that of Example X1, with the difference being that the amount of oxygen storage material coated on the coated electrolyte particles was different, and can be seen in Table 2.

[0461] Examples X9 to X10. Type of sulfide electrolyte in coated electrolyte particles Changed

[0462] Coated electrolyte particles, anode film sheets, and an all-solid-state battery were prepared using a method basically identical to that of Example X1, the difference being that the type of sulfide electrolyte in the coated electrolyte particles was different, and in Example X9, LGPS-type sulfide electrolyte Li 10 GeP2S 12 It was used, and in Example X10, 75Li2S-25P2S5, that is, a lithium sulfide-phosphorus pentasulfide complex type sulfide electrolyte (75Li2S)·(25P2S5), was used, and can be seen in Table 2.

[0463] Examples X11 to X12. of coated electrolyte particles D v 50 Changed.

[0464] Coated electrolyte particles, anode film sheets, and all-solid-state batteries were prepared using a method basically identical to that of Example X1, with the difference being the use of sulfide electrolyte materials with different particle sizes D v 50 different coated electrolyte particles were manufactured. Refer to Table 2.

[0465] Examples X13. Anode In the active material layer The capacity of the coated electrolyte particles was changed.

[0466] Coated electrolyte particles, anode film sheets, and an all-solid-state battery were prepared using a method essentially identical to that of Example X1, the difference being that the capacity of the coated electrolyte particles in the anode active material layer was different, and in the case where the total weight ratio of the anode electrolyte particles in the anode active material layer was the same, 8 wt% Li was used instead of the coated electrolyte particles in Example X1. 5.5 PS 4.5 Cl 1.5 A sulfide solid electrolyte was used, namely coated electrolyte particles (2 wt% La2O2SO4-coated Li5 . 5PS4. 5Cl1 .5 sulfide electrolytes) and sulfide-based electrolytes without an oxygen storage layer (Li 5.5 PS 4.5 Cl 1.5 A mixture of ) was used as the anode electrolyte particles; in the step of manufacturing the anode film sheet, the weight ratio of the anode active particles, coated electrolyte particles, sulfide-based electrolyte without an oxygen storage layer, conductive agent VGCF, and adhesive was 85:5:8:1:1. Refer to Table 2.

[0467] Examples X14. bipolar layer and solid The electrolyte layer Solid electrolytes were provided using all coated electrolyte particles.

[0468] Electrolyte particles, anode film sheets, solid electrolyte film sheets, and all-solid-state batteries were prepared using a method basically identical to that of Example X1, with the difference being that the composition of the solid electrolyte film sheets was different and Li5 . 5PS4 . 5Cl1 .5 Instead, the coated electrolyte particles in Example X1 (2 wt% La2O2SO4-coated Li5 . 5PS4 . 5Cl1 .5 It is said that a sulfide electrolyte was used. Refer to Table 2.

[0469] Electrolyte particles coated in an argon atmosphere (2 wt% La2O2SO4-coated Li5 . 5PS4 . 5Cl1 .5 100 mg of sulfide electrolyte was weighed and added to a battery mold and pressurized to obtain a solid electrolyte membrane, and then an anode membrane sheet prepared using the same method as in Example X1 was placed on one side of the solid electrolyte membrane, and an InLi alloy was laminated as a cathode layer on the other side to assemble an all-solid-state battery.

[0470] Examples X15. The anode layer It includes simultaneously coated positively active particles and coated electrolyte particles.

[0471] Coated electrolyte particles, anode film sheets, and an all-solid-state battery were prepared using a method essentially identical to that of Example X1, with the difference being the composition of the anode film sheet; specifically, instead of the anode active particle raw material (NCM811) in the anode film sheet of Example X1, coated anode active particles (2 wt% YBaCo4O7-coated NCM811 anode active particles) prepared by the same method as Example 1 were used; that is, coated sulfide electrolyte (2 wt% La2O2SO4-coated Li5) prepared by the same method as Example X1 . 5PS4 . 5Cl1 .5 A sulfide electrolyte was used as the anode electrolyte particle, and coated anode active particles (2 wt% YBaCo4O7-coated NCM811 anode active particles) prepared in the same manner as in Example 1 were used as the anode active particles. When preparing the anode film sheet, the weight ratio of the anode active particles, anode electrolyte particles, conductive agent, and adhesive is still 85:13:1:1. Refer to Table 2.

[0472] Examples X16. The anode layer It includes simultaneously coated positively active particles and coated electrolyte particles, and a solid The electrolyte layer It includes coated electrolyte particles.

[0473] Coated electrolyte particles, anode film sheets, solid electrolyte film sheets, and all-solid-state batteries were prepared using a method basically identical to that of Example X1, with the difference being that the composition of the anode film sheets and solid electrolyte film sheets was different. Refer to Table 2.

[0474] (1) The composition of the anode film sheet was different, and instead of the anode active particle raw material (NCM811) in the anode film sheet of Example X1, coated anode active particles (2 wt% YBaCo4O7-coated NCM811 anode active particles) prepared in the same manner as Example 1 were used; that is, coated sulfide electrolyte (2 wt% La2O2SO4-coated Li) prepared in the same manner as Example X1 5.5 PS 4.5 Cl 1.5 A sulfide electrolyte was used as the anode electrolyte particle, and coated anode active particles (2 wt% YBaCo4O7-coated NCM811 anode active particles) prepared in the same manner as in Example 1 were used as the anode active particles. When preparing the anode film sheet, the weight ratio of the anode active particles, anode electrolyte particles, conductive agent, and adhesive is still 85:13:1:1.

[0475] (2) The composition of the solid electrolyte membrane sheet was different. Li5 . 5PS4 . 5Cl1 .5 Instead, the coated electrolyte particles in Example X1 (2 wt% La2O2SO4-coated Li5 . 5PS4 . 5Cl1 .5 A sulfide electrolyte was used.

[0476] Electrolyte particles coated in an argon atmosphere (2 wt% La2O2SO4-coated Li5 . 5PS4 . 5Cl1 .5 100 mg of sulfide electrolyte was weighed and added to a battery mold and pressurized to obtain a solid electrolyte film, and then a positive electrode film sheet prepared using this example was placed on one side of the solid electrolyte film, and an InLi alloy was laminated as a negative electrode on the other side to assemble an all-solid-state battery.

[0477] Comparative example X1. The anode electrolyte particles have no arbitrary coating layer, i.e., oxygen storage layer does not exist.

[0478] A positive film sheet and an all-solid-state battery were manufactured using a method essentially identical to that of Example X1, the difference being that the positive electrolyte particles used in the manufacture of the positive film sheet were different, and the positive electrolyte particles in this example were Li5 without any surface coating. . 5PS4 . 5Cl1 .5 It is a sulfide electrolyte.

[0479] Comparative example X2 to X3. The anode electrolyte particles are provided with a coating layer, but oxygen storage layer None; instead of oxygen storage materials Non-oxygen It was coated using storage materials.

[0480] Comparative Example X2 manufactured an anode film sheet and an all-solid-state battery using essentially the same method as Example X1, the difference being that the anode electrolyte particles used were 2 wt% La2O2SO4-coated LGPS-type sulfide electrolyte Li 10 GeP2S 12 And, the thickness of the La2O2SO4 coating layer is approximately 2 nm. The anode electrolyte particles are "2 wt% La2O2SO4-coated Li 10 GeP2S 12 It can be written as "

[0481] Comparative Example X3 manufactured an anode film sheet and an all-solid-state battery using basically the same method as Example X1, the difference being that the anode electrolyte particles used were 2 wt% La2O2SO4-coated lithium sulfide-phosphorus pentasulfide complex type sulfide electrolyte 75Li2S-25P2S5, and the thickness of the La2O2SO4 coating layer was about 2 nm. The anode electrolyte particles can be described as "2 wt% La2O2SO4-coated 75Li2S-25P2S5".

[0482] Comparative example X4. Solid Electrolyte In the case of materials Oxygen in the form of a coating Storage layer Instead, oxygen storage materials were introduced using a physical mixing method.

[0483] Comparative Example X4 manufactured an anode film sheet and an all-solid-state battery using basically the same method as Example X1, the difference being that the step of manufacturing coated electrolyte particles was omitted and the composition of the anode film sheet was different.

[0484] In Comparative Example X4, La2O2SO40.2g(D v 50 is approximately 200nm) and Li5 . 5PS4 . 5Cl1 .5 10g of sulfide solid electrolyte was ground and mixed in a mortar to obtain La2O2SO4-mixed and doped Li5 . 5PS4 . 5Cl1 .5 Electrolyte material was obtained. Then, LiNiO . 8Co0 . 1Mn0 . 1O2(NCM811) positively active particles (D v 50 is 4μm), anode electrolyte particles (previously prepared La2O2SO4-mixed and doped Li5 . 5PS4 . 5Cl1 .5 Electrolyte material), conductive agent VGCF, and adhesive PTFE were each weighed in a weight ratio of 85:13:1:1 and uniformly mixed in a dual planetary mixer. Then, the uniformly mixed powder was heated and pressurized in an internal mixer to form a lump-shaped material, and then hot-rolled at 80°C to produce a self-standing anode sheet. Finally, an anode film sheet was obtained by hot-rolling and combining it with aluminum foil, which is an anode current collector.

[0485] Table 2. Relevant parameters of coated electrolyte particles

[0486] Oxygen storage layer Oxygen storage layer of coated electrolyte particles Chemical formula of sulfide electrolyte in solid electrolyte body D of coated electrolyte particles v 50 Chemical formula of oxygen storage material Weight ratio of coated particles of oxygen storage material Oxygen storage layer thickness Example X1 La2O2SO4 2 wt% 2nm Li5 . 5PS4 . 5Cl1 .5 1μm Example X2 YBaCo4O7 2 wt% 2nm Li5 . 5PS4 . 5Cl1 .5 1μm Example X3 La0 . 8Sr0 . 2CoO3 1 wt% 2nm Li5 . 5PS4 . 5Cl1 .5 1μm Example X4 Ce0 . 6Zr0 . 3Al0 . 1O1 .95 1 wt% 2nm Li5 . 5PS4 . 5Cl1 .5 1μm Example X5 La2O2SO4 0.5 wt% Approximately 0.5nm Li5 . 5PS4 . 5Cl1 .5 1μm Example X6 La2O2SO4 5 wt% Approximately 6nm Li5 . 5PS4 . 5Cl1 .5 1μm Example X7 La2O2SO4 0.1 wt% Approximately 0.1 nm Li5 . 5PS4 . 5Cl1 .5 1μm Example X8 La2O2SO4 10 wt% Approximately 12 nm Li5 . 5PS4 . 5Cl1 .5 1μm Example X9 La2O2SO4 2 wt% 2nm That 10 GeP2S 12 1μm Example X10 La2O2SO4 2 wt% 2nm 75Li2S-25P2S5 1μm Example X11 La2O2SO4 2 wt% 2nm Li5 . 5PS4 . 5Cl1 .5 Approximately 50nm Example X12 La2O2SO4 2 wt% 2nm Li5 . 5PS4 . 5Cl1 .5 Approximately 5μm Example X13 La2O2SO4 2 wt% 2nm Li5 . 5PS4 . 5Cl1 .5 1μm Example X14 La2O2SO4 2 wt% 2nm Li5 . 5PS4 . 5Cl1 .5 1μm Example X15 Coated sulfide electrolyte identical to Example X1 + coated anode active particles identical to Example 1 Example X16 Coated sulfide electrolyte identical to Example X1 + coated anode active particles identical to Example 1

[0487] In Table 2, the anode active particles of the anode layers in Examples X1 to X14 are all NCM811 without an oxygen storage layer; and the solid electrolyte layer in Examples X14 and X16 is 2 wt% La2O2SO4-coated Li5 . 5PS4. 5Cl1 .5 ...was used, and in the remaining examples, the solid electrolyte layer was Li5 without an oxygen storage layer. . 5PS4 . 5Cl1 .5 used

[0488] B. Test Method

[0489] The electrochemical performance of the positive electrode sheet and the corresponding all-solid-state battery was tested using a solid-state molded battery, and the test window of the battery is 2.8 to 4.3 V (based on lithium potential).

[0490] 1. Test of H2S emission from solid electrolyte materials

[0491] In a dew point environment of -55°C, 100 mg of electrolyte powder is uniformly plated in a 5 cm diameter Petri dish, and then the Petri dish containing the electrolyte powder is placed into a 50 L box through a sealed transfer box. The sealed transfer box of the Petri dish containing the electrolyte powder is quickly opened, and the 50 L box is sealed. A hydrogen sulfide sensor (PGM-2500) is installed in the box to record the cumulative value of hydrogen sulfide in real time within the 50 L box, and the reaction is allowed until the detection value of the hydrogen sulfide sensor no longer increases, which indicates that the electrolyte has completely reacted with water molecules within the box; at the same time, a fan with a blade diameter of 8 cm is installed in the box. Since the density of hydrogen sulfide is greater than that of air, the fan prevents the settling of hydrogen sulfide gas and ensures that the hydrogen sulfide gas within the 50 L box is uniformly distributed, thereby ensuring the reliability of the hydrogen sulfide gas concentration test. Before the test, a 50L box was placed in an environment with a relative humidity of 70%RH.

[0492] You can refer to "Ionic conductivity of coated electrolyte particles" in Table 4.

[0493] 2. Ionic conductivity test of solid electrolyte materials

[0494] Ionic conductivity was primarily measured via AC impedance spectroscopy (EIS). The detailed procedure is as follows: 120 mg of solid electrolyte powder was poured into a 10 mm diameter tablet mold and compressed into a dense circular sheet at 360 MPa; then, the solid electrolyte membrane sheet was clamped in the mold at 120 MPa using a 10 mm diameter cylindrical stainless steel current collector; subsequently, the current collector was connected to an electrochemical workstation, and a bias voltage of 10 mV, 10 Hz to 10 6 Electrochemical impedance spectroscopy (EIS) was performed on the solid electrolyte membrane sheet in the frequency range of Hz. The curve of the electrochemical impedance spectrum ranges from high to low frequencies, and the intersection point with the Z'-axis is recorded as the resistance value R, and the ionic conductivity can be calculated using formula (1):

[0495] (1)

[0496] Here, d is the thickness of the solid electrolyte membrane sheet and A is the contact area between the solid electrolyte membrane sheet and the current collector.

[0497] You can refer to "amount of H2S released from coated electrolyte particles" in Table 4.

[0498] 3. Initial discharge capacity

[0499] The test procedure is as follows: The assembled all-solid-state battery was charged to 3.68V (4.3V based on lithium potential) at a current density of 0.1C and left for 10 minutes, and then discharged to 2.18V (2.8V based on lithium potential) at a current density of 0.1C to determine the initial discharge capacity of the battery. The battery was tested at 25±3°C, where 1C = 200mA / g.

[0500] You can refer to the "0.1C discharge capacity" in Table 3 and the "initial discharge capacity" in Table 4.

[0501] 4. Initial Coulombic Efficiency

[0502] The initial Coulomb efficiency of the battery can be calculated by dividing the initial discharge capacity obtained from testing at 0.1C by the initial charge capacity.

[0503] 5. Magnification Performance

[0504] The test procedure is as follows: the charge scale of the all-solid-state battery is fixed at 0.1C, then discharged at scales of 0.1C, 0.33C, 1C, 2C, and 3C, cycled three times for each scale, and the battery voltage test window is 2.8 to 4.3V vs. Li + / Li, and the battery was tested at 25±3°C, where 1C=200mA / g.

[0505] 6. Cycle Performance

[0506] The assembled all-solid-state battery was first subjected to three constant-current charge-discharge cycles at a current density of 0.1C to determine the initial discharge capacity and initial Coulomb efficiency. Subsequently, a long-cycle test was performed by cycling the battery 200 times at a current density of 0.33C to calculate the battery's cycle capacity retention rate. The battery voltage test window was 2.8 to 4.3V vs. Li + / Li, and the battery was tested at 25±3°C, where 1C=200mA / g.

[0507] C. Test Analysis Results

[0508] You can refer to Table 3 for the test results.

[0509] In Examples 1 to 14, the anode layer comprises all coated positive active particles, in Examples X1 to X13, the anode layer comprises all coated electrolyte particles, in Example X14, the anode layer and the solid electrolyte layer comprise all coated electrolyte particles, in Example X15, the anode layer comprises coated positive active particles and coated electrolyte particles, in Example X16, the anode layer comprises coated positive active particles and coated electrolyte particles, and the solid electrolyte layer also comprises coated electrolyte particles, and the solid battery prepared in each example has superior discharge capacity and cycle performance, superior scaling performance, and furthermore, superior initial Coulomb efficiency. Therefore, by using an oxygen storage material to coat at least one of positive active particles or a sulfide-based electrolyte, all electrochemical performances, such as discharge capacity, scaling performance, and cycle performance of the sulfide solid battery, can be improved.

[0510] According to the experimental results of Examples X1 to X16, after coating a sulfide-based electrolyte with an oxygen storage material, the amount of hydrogen sulfide released can be significantly reduced, air stability can be significantly improved, and at the same time, good ionic conductivity can be achieved. A sulfide solid battery manufactured with the corresponding coated electrolyte particles has superior discharge capacity and cycle performance, superior scaling performance, and even superior initial Coulomb efficiency.

[0511] In addition, the battery voltage test window is 2.8 to 4.3V vs. Li + / Li, and therefore, the ratio significantly improved the stability of the sulfide solid-state battery during high-voltage operation.

[0512] Compared to Examples 1 to 9, an oxygen storage layer was not installed in the positive active particles of Comparative Example 1, so the discharge capacity, initial Coulomb efficiency, scaling performance, and cycle capacity retention rate of the sulfide solid battery of Comparative Example 1 were all significantly deteriorated, and the cycle performance was severely deteriorated.

[0513] Compared to Example 1, the positive active particles of Comparative Examples 2 and 3 were coated with an oxygen-free storage material, and the discharge capacity, initial Coulomb efficiency, scaling performance, and cycle capacity retention rate were all deteriorated to different degrees.

[0514] Compared to Example 1, when using a positively active particle having an oxygen storage material mixed and doped with the positive layer of Comparative Example 4, the discharge capacity, initial Coulomb efficiency, scaling performance, and cycle capacity retention rate were all deteriorated to different degrees.

[0515] Compared to Examples X1 to X8, the oxygen storage layer was not installed in the anode electrolyte particles of Comparative Example X1, so the hydrogen sulfide emission amount increased significantly, and the discharge capacity, initial Coulomb efficiency, and cycle capacity retention rate of the sulfide solid battery of Comparative Example X1 all significantly deteriorated, and the cycle performance deteriorated very severely.

[0516] Compared to Example X1, the anode electrolyte particles of Comparative Examples X2 to X3 were coated with an oxygen-free storage material, and the hydrogen sulfide emission was significantly increased, and the initial discharge capacity, initial Coulomb efficiency, and cycle capacity retention rate were all deteriorated to different degrees.

[0517] Compared to Example X1, when using anode electrolyte particles having an oxygen storage material mixed and doped with the anode layer of Comparative Example X4, the hydrogen sulfide emission was significantly increased, and the initial discharge capacity, initial Coulomb efficiency, and cycle capacity retention rate were all deteriorated to different degrees.

[0518] Table 3. Test results of Examples 1 to 14 and Comparative Examples 1 to 4

[0519] turn 0.1C discharge capacity (mAh / g) Initial Coulomb efficiency (%) 0.33C discharge capacity (mAh / g) 1C discharge capacity (mAh / g) 2C discharge capacity (mAh / g) 3C discharge capacity (mAh / g) Dose retention rate (0.33C) after 200 cycles (%) Example 1 205.4 88.0 195.5 182.3 161.2 150.7 94.7 Example 2 200.5 86.3 190.7 177.8 155.1 143.6 90.3 Example 3 198.2 87.6 188.6 175.3 152.4 139.7 91.5 Example 4 203.7 87.7 193.6 180.4 158.9 148.6 94.3 Example 5 207.6 88.4 197.3 184.5 163.6 152.8 95.4 Example 6 194.3 84.5 183.2 170.4 148.6 134.3 86.7 Example 7 192.5 85.6 181.6 168.2 145.1 131.6 88.4 Example 8 185.4 82.5 175.3 161.5 137.4 123.7 80.2 Example 9 186.5 84.7 176.4 163.3 138.5 124.9 85.3 Example 10 146.8 92.5 141.5 132.7 120.2 109.7 96.5 Example 11 250.6 84.6 237.7 221.3 200.5 179.3 94.6 Example 12 212.3 87.8 201.5 188.6 166.4 154.7 90.8 Example 13 192.1 87.5 182.2 170.3 147.4 135.5 96.7 Example 14 191.4 85.4 181.6 167.5 144.6 133.7 85.8 Comparative Example 1 178.2 75.6 160.3 137.6 114.5 85.4 65.3 Comparative Example 2 189.5 83.4 175.3 148.9 126.3 100.6 75.8 Comparative Example 3 190.6 83.8 177.6 150.8 130.6 110.7 79.8 Comparative Example 4 188.5 80.6 174.1 146.4 123.5 97.6 74.6

[0520] Table 4. Test results of Examples X1 to X16 and Comparative Examples X1 to X4

[0521] turn Ionic conductivity of coated electrolyte particles (mS / cm) H2S emission from coated electrolyte particles (cm²) 3 / g) Initial discharge capacity (mAh / g) Initial Coulomb efficiency (%) Dose retention rate (%) after 200 cycles Example X1 4.82 9.8 208.5 89.7 96.5 Example X2 4.78 10.4 206.6 88.5 95.2 Example X3 4.81 11.5 205.2 88.3 94.7 Example X4 4.79 12.3 202.8 87.9 93.8 Example X5 4.90 20.4 195.3 84.5 86.6 Example X6 4.05 8.5 196.8 87.6 92.5 Example X7 4.98 31.2 186.4 82.4 76.4 Example X8 3.12 6.8 192.6 83.7 90.6 Example X9 7.54 12.8 209.6 88.6 95.3 Example X10 0.54 11.6 197.5 86.4 92.4 Example X11 1.03 11.3 210.4 87.6 97.4 Example X12 8.02 8.7 185.2 84.5 87.5 Example X13 4.87 15.8 190.3 85.3 85.5 Example X14 4.82 9.8 210.6 89.8 97.3 Example X15 4.82 9.8 211.5 90.4 97.6 Example X16 4.82 9.8 213.6 91.5 98.2 turn Ionic conductivity (mS / cm) of sulfide electrolytes used in solid electrolyte layers H2S emission amount from sulfide electrolytes used in solid electrolyte layers (cm²) 3 / g) Initial discharge capacity (mAh / g) Initial Coulomb efficiency (%) Dose retention rate (%) after 200 cycles Comparative Example X1 5.03 48 180.7 78.9 68.9 Comparative Example X2 7.72 59 182.4 77.6 65.8 Comparative Example X3 0.72 52 170.6 75.4 63.4 Comparative Example X4 4.8 36 185.7 80.3 75.8

[0522] In addition, coated electrolyte particles (e.g., coated electrolyte particles in Example X1) are used in the solid electrolyte layer, and anode active particles having a conventional coated structure and anode electrolyte particles not coated with an oxygen storage material are used in the anode layer, thereby improving the electrochemical performance, such as scaling performance and cycle performance of the solid-state battery.

[0523] The above description of each embodiment tends to emphasize the differences between the embodiments, and identical or similar points may be referenced to one another; for the sake of brevity, they are not further described herein. Each technical feature of the embodiments described above may be combined arbitrarily, and for the sake of simplicity of description, not all possible combinations of each technical feature among the embodiments described above are described; however, as long as there is no contradiction in such combinations of technical features, they should all be deemed to be within the scope of the description in this specification. It must be explained that this application is not limited to the embodiments described above. The embodiments described above are merely examples, and any embodiments having substantially the same configuration as the technical concept and exhibiting the same functional effect within the scope of the technical solution of this application are included within the technical scope of this application. The embodiments described above are merely representations of the embodiments of this application, and while the descriptions thereof are more detailed, they should not be interpreted as limiting the scope of the patent. In addition, within the scope of this application, various modifications conceivable by a person skilled in the art to the embodiments without departing from the intent of this application, and other methods constructed by combining some components of the embodiments are also included within the scope of this application. Explanation of the symbols

[0524] 80, coated particle; 82, particle body; 84, oxygen storage layer; 842, oxygen storage material; 810, coated electrolyte particle; 812, solid electrolyte body; 820, coated anode active particle; 822, anode active body; 910, sulfide-based electrolyte without oxygen storage layer; 920, anode active particle without oxygen storage layer; 200, anode layer; 20, anode film; 210, anode current collector; 220, anode active material layer; 220a, anode active material layer comprising coated electrolyte particle; 220b, anode active material layer comprising coated anode active particle; 220c, anode active material layer comprising coated electrolyte particle and coated anode active particle; 220d, anode active material layer comprising coated anode active particle and sulfide-based electrolyte without oxygen storage layer; 220e, a positive active material layer comprising a positive active particle without a coated electrolyte particle and an oxygen storage layer; 100, a solid electrolyte layer; 100a, a solid electrolyte layer comprising a coated electrolyte particle; 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 a coated electrolyte particle; 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 box body; 3, a lower box body; 4, a battery module; 5, a solid battery cell; 51, a case; 52, a solid cell; 53, a cover plate; 6, an electric device. In each drawing, a solid cell (52), an anode film (20), an anode current collector (210), an anode active material layer (220), an anode layer (200), an anode active material layer (220a) containing coated electrolyte particles, an anode active material layer (220b) containing coated anode active particles, an anode active material layer (220c) containing coated electrolyte particles and coated anode active particles, an anode active material layer (220d) containing coated anode active particles and a sulfide-based electrolyte without an oxygen storage layer, an anode active material layer (220e) containing coated electrolyte particles and anode active particles without an oxygen storage layer, a solid electrolyte layer (100), a solid electrolyte layer (100a) containing coated electrolyte particles, a solid electrolyte layer (100b) containing a sulfide-based electrolyte without an oxygen storage layer, a solid electrolyte film (10), a solid electrolyte film (10a) containing coated electrolyte particles, a solid electrolyte film (10b) containing a sulfide-based electrolyte without an oxygen storage layer, a cathode layer (300), etc. The drawn dimensions of the structure do not represent actual dimensions; and in each drawing, the shape and dimensions of the material or local structure of the material, such as the related coated particle (80), particle body (82), oxygen storage layer (84), oxygen storage material (842), coated electrolyte particle (810), solid electrolyte body (812), coated anode active particle (820), anode active body (822), sulfide-based electrolyte without oxygen storage layer (910), anode active particle without oxygen storage layer (920), etc., do not represent or are not used to limit the shape and dimensions of the actual material, and it can be understood that the number of drawings does not represent or is not used to limit the actual quantity and quantity proportion.

Claims

Claim 1 A solid battery material comprising coated particles, wherein the coated particles comprise 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; wherein the coated particles comprise at least one of a coated positively active particle and a coated electrolyte particle; where the coated particles are the coated positively active particles, the particle body is a positively active body and the positively active body comprises a positively active material; and where the coated particles are the coated electrolyte particles, the particle body is a solid electrolyte body and the solid electrolyte body comprises a sulfide electrolyte. Claim 2 In claim 1, the oxygen storage material comprises one or more of a lanthanide metal sulfate oxygen storage material, a yttrium barium cobalt oxide oxygen storage material, and a perovskite oxygen storage material, a solid battery material. Claim 3 In paragraph 2, the oxygen storage material is the lanthanide metal sulfate type oxygen storage material having the chemical formula Ln2O2SO4 - δ1 A phosphorus oxygen storage material comprising, wherein Ln is a lanthanide metal element, and the lanthanide metal element comprises one or more elements selected from La, Ce, Pr, Nd, Sm, Eu, Gd, and Tb, and 0≤δ1≤4; the yttrium barium cobalt oxide type oxygen storage material has the chemical formula (Y x M1 (1-x) )(Ba y M2 (1-y) )(Co z M3 (1-z) )4O 7+δ2 The oxygen storage material comprises, wherein M1 is selected from one or more elements among Ca, In, Dy, Ho, Er, Tm, Yb, and Lu, M2 is Sr, and M3 is selected from one or more elements among Mn, Fe, Ni, Cu, Zn, Al, Ga, and Zr, and 0≤x≤1, 0≤y≤1, 0≤z≤1, and 0≤2≤1.5; the perovskite-type oxygen storage material has the chemical formula La1 - a A a Mn1 - b B b O3 - δ3 A solid-state battery material comprising a phosphorus oxygen storage material, wherein A is selected from one or more elements among Sr, Y, Ce, Pr, and Nd, B is selected from one or more elements among Ni, Fe, Cu, and Co, and satisfies one or more of the characteristics such as 0≤a≤1, 0≤b≤1, and 0≤3≤1. Claim 4 A solid battery material according to any one of claims 1 to 3, wherein the weight ratio of the oxygen storage material in the coated particles is 0.1% to 10% by weight, and optionally 0.5% to 5% by weight. Claim 5 A 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 optionally 0.5 nm to 10 nm. Claim 6 A solid battery material according to any one of claims 1 to 5, wherein the oxygen storage material comprises oxygen storage particles, and the particle size of the oxygen storage particles is 1 nm to 100 nm. Claim 7 A solid battery material according to claim 6, wherein the particle size of the oxygen storage particles is 1 nm to 50 nm. Claim 8 A solid battery material according to any one of claims 1 to 7, wherein the particle size of the positive active body is 0.1 μm to 20 μm, and optionally 1 μm to 10 μm. Claim 9 In claim 8, D of the coated anodic active particles v 50 is 0.1 μm to 20 μm, optionally 1 μm to 10 μm; where, D v 50 represents the particle size corresponding when the cumulative volume distribution percentage of a multi-particle mixture reaches 50%, a solid battery material. Claim 10 A solid battery material according to any one of claims 1 to 9, wherein the positive electrode active material comprises an oxide positive electrode active material; optionally, the oxide positive electrode active material comprises a lithium transition metal oxide. Claim 11 In claim 10, the lithium transition metal oxide comprises one or more of a lithium cobalt oxide-type cathode active material, a high nickel cathode active material, a lithium-rich manganese-based cathode active material, and a modified form of any of the aforementioned cathode active materials, wherein the modified form comprises one or more of doping modification and coating modification; optionally, the lithium cobalt oxide-type cathode active material comprises a Li element, a Co element, and an O element, wherein the atomic molar ratio of the Co element and the O element is x2:2 and satisfies 0.9 ≤ x2 ≤ 1; optionally, the lithium cobalt oxide-type cathode active material comprises a Li element, a Co element, and an O element with an atomic molar ratio of 1:x2:2 and satisfies 0.9 ≤ x2 ≤ 1; and the high nickel cathode active material comprises a Li element, a Ni element, and an O element, wherein the atomic molar ratio of the Ni element and the O element is y2:2 and satisfies 0.6 ≤ y2 ≤ 1; Optionally, the high-nickel cathode active material comprises Li, Ni, and O elements with an atomic molar ratio of 1:y2:2 and satisfies 0.6≤y2≤1; and the lithium-rich manganese-based cathode active material comprises Li, Mn, and O elements with an atomic molar ratio of (1+p):(p+r(1-p)):(2+p) and 0 <p≤1, 0≤r≤1을 충족하는, 고체 전지 재료. Claim 12 In claim 11, the lithium transition metal oxide is a solid battery material satisfying one or more of the characteristics 0.8≤y2≤1; 0.2≤p≤1. Claim 13 In claim 11 or 12, the lithium transition metal oxide is the lithium cobalt oxide type cathode active material having the chemical formula LiCo x2 R1 - x2 It comprises a lithium transition metal oxide of O2, wherein R is selected from one or more elements among Ni, Mg, Ti, Al, Cr, Fe, Nb, and Ta; the high-nickel cathode active material has the chemical formula LiNi y2 Co z2 D1 -y2- z2 A solid battery material satisfying one or more of the following characteristics: comprising a lithium transition metal oxide of O2, wherein 0≤z2≤0.4, 0.6≤=(y2+z2)≤=1, and D is selected from one or more elements among Mn, Al, Zr, La, Ce, Ti, Mg, Nb, Ta, Mo, and W; optionally, D comprises the element Mn; and the lithium-rich manganese-based cathode active material comprises a lithium transition metal oxide having the chemical formula pLi2MnO3·(1-p)LiZO2, wherein Z is selected from one or more elements among Ni, Co, Mn, Cr, Fe, Al, Nb, Mo, and Ru. Claim 14 A solid 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 optionally 50 nm to 5 μm. Claim 15 In any one of claims 1 to 14, D of the coated electrolyte particles v 50 is 1 nm to 20 μm, optionally 50 nm to 5 μm; D v 50 represents the particle size corresponding when the cumulative volume distribution percentage of a multi-particle mixture reaches 50%, a solid battery material. Claim 16 A solid battery material according to any one of claims 1 to 15, wherein the sulfide electrolyte comprises one or more of an argyrodite-type sulfide electrolyte, an LGPS-type sulfide electrolyte, and a lithium sulfide-phosphorus pentasulfide complex-type sulfide electrolyte. Claim 17 In paragraph 16, the above sulfide electrolyte is the above argyrodite-type sulfide electrolyte, the chemical formula is Li6 ± s P1 - j A j S5 ±s- t B t X1 ± s It comprises a phosphorus sulfide electrolyte, wherein 0≤j<1, 0≤t<1, 0≤s<1, A is selected from one or more elements among Ge, Si, Sn, and Sb, B is one or more elements among O, Se, and Te, and X is selected from one or more elements among Cl, Br, I, and F; the LGPS-type sulfide electrolyte has the chemical formula Li 10 ± δ5 Ge1 - g G g P2 - q Q q S 12 - w W w A phosphorus sulfide electrolyte comprising, wherein 0≤δ5<1, 0≤g≤1, 0≤q≤2, 0≤w<1, G is selected from one or two elements among Si and Sn, Q is Sb, and W is selected from one or more elements among O, Se, Te, Cl, Br, I, and F; the lithium sulfide-phosphorus pentasulfide complex type sulfide electrolyte is (100-uv)Li2S·uP2S5·vM m N n Contains a phosphorus sulfide electrolyte, where 0 <u<100, 0≤v<100, 0≤u+v<100, 0≤m<4, 0≤n<6이고, M은 Li, B, Ge, Si, Sn 및 Sb 중 하나 이상의 원소에서 선택되고, N은 S, Se, Te, O, Cl, Br, I 및 F 중 하나 이상의 원소에서 선택되는 것과 같은 특징 중 하나 이상을 충족하는, 고체 전지 재료. Claim 18 A solid battery material according to any one of claims 1 to 17, wherein the solid battery material is a sulfide solid battery material. Claim 19 A solid battery material according to any one of claims 1 to 18, wherein the solid battery material is a sulfide all-solid-state battery material. Claim 20 A positive active material layer comprising a solid battery material according to any one of claims 1 to 19. Claim 21 In claim 20, the anode active material layer comprises anode active particles; the anode active particles comprise coated anode active particles, wherein the weight ratio of the coated anode active particles in the anode active material layer is 70% to 99% by weight, and optionally 80% to 95% by weight. Claim 22 The anode active material layer according to claim 20 or 21, wherein the anode active material layer comprises anode electrolyte particles; the anode electrolyte particles comprise coated electrolyte particles, and the weight ratio of the coated electrolyte particles in the anode active material layer is 0.1% to 30% by weight, and optionally 5% to 20% by weight. Claim 23 A positive film comprising a positive active material layer, wherein the positive active material layer comprises a solid battery material according to any one of claims 1 to 19, or the positive active material layer is a positive active material layer according to any one of claims 20 to 22. Claim 24 A solid electrolyte membrane comprising a solid battery material according to any one of claims 1 to 7 and 14 to 19, wherein the coated particles are the coated electrolyte particles. Claim 25 A solid battery comprising a positive electrode layer, a solid electrolyte layer, and a negative electrode layer; wherein the solid battery satisfies one or more of the following features: the positive electrode layer comprises a positive active material layer according to any one of claims 20 to 22; the positive electrode layer comprises a positive film according to claim 23; and the solid electrolyte layer comprises a solid electrolyte film according to claim 24. Claim 26 A solid battery comprising a positive electrode layer, a solid electrolyte layer, and a negative electrode layer; wherein the solid battery comprises one or more solid battery materials according to any one of claims 1 to 19; wherein, where the coated particles comprise the coated positive electrode active particles, the coated positive electrode active particles are located in the positive electrode layer; and wherein, where the coated particles comprise the coated electrolyte particles, the coated electrolyte particles are located in at least one of the positive electrode layer and the solid electrolyte layer. Claim 27 A solid battery comprising a positive electrode layer, a solid electrolyte layer, and a negative electrode layer; wherein the positive electrode layer comprises a positive electrode active material layer, and the positive electrode active material layer comprises positive electrode active particles and positive electrode electrolyte particles; wherein at least one of the solid electrolyte layer and the positive electrode electrolyte particles comprises a sulfide electrolyte; wherein the solid battery comprises one or more solid battery materials according to any one of claims 1 to 19; wherein at least a portion of the positive electrode electrolyte particles comprises a sulfide electrolyte, and the positive electrode active material layer comprises at least one of the coated positive electrode active particles and the coated electrolyte particles; and wherein the solid electrolyte layer comprises the coated electrolyte particles, satisfying at least one of these features. Claim 28 A solid battery according to claim 27, wherein the solid electrolyte layer and the anode electrolyte particles both comprise a sulfide electrolyte, the sulfide electrolyte contained in the anode electrolyte particles is denoted as a first sulfide electrolyte, the sulfide electrolyte contained in the solid electrolyte layer is denoted as a second sulfide electrolyte, and the first sulfide electrolyte and the second sulfide electrolyte may be the same or different; satisfying one or more of the features such as the anode electrolyte particles comprising a sulfide electrolyte and at least one of the anode active particles and the anode electrolyte particles comprising the coated particles. Claim 29 A solid battery according to any one of paragraphs 25 to 28, wherein the solid battery is a sulfide solid battery. Claim 30 A solid battery according to any one of claims 25 to 29, wherein the solid battery is a sulfide all-solid-state battery. Claim 31 An electric device comprising a solid-state battery according to any one of claims 25 to 30. Claim 32 Application of a solid battery material according to any one of claims 1 to 19, or a positive active material layer according to any one of claims 20 to 22, or a positive film according to claim 23, or a solid electrolyte film according to claim 24 in the manufacture of a solid battery, optionally, said solid battery is a sulfide solid battery; more optionally, said solid battery is a sulfide all-solid battery.

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