All-solid-state battery-coated halide cathode composite material, its manufacturing method, and applications

Abstract

To provide an all-solid battery coating type halogenization cathode composite material, a manufacturing method of the same, and an all-solid battery.SOLUTION: A manufacturing method of a coating type halogenization cathode composite material, includes: a step of solving a metal halogenization of a constant mass ratio and a halogenization solid electrolyte into a deionized water, and manufacturing a metal salt aqueous solution; and a step of performing drying and manufacturing of a particle by using spray drying processing, and spraying the obtained metal salt aqueous solution to a high temperature chamber, and finally forming a spherical type positive electrode composite material of which an inner core is a metal halogenization material and an outer layer is the halogenization solid electrolyte by using a feature that a solute dissolution level is different. A dissolution level of the metal halogenization material is lower than that of the halogenization solid electrolyte. A positive electrode material in the present invention indicates a good electric chemical performance.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to the technical field of all-solid-state battery technology, and specifically relates to an all-solid-state battery-coated halide cathode composite material, a manufacturing method thereof, and an application thereof.

Background Art

[0002] Currently, the power source with a high market share is a lithium-ion battery. The specific capacity of its positive and negative electrode materials is low, which significantly limits the energy density of the battery system. In addition, a large amount of organic liquid electrolyte is used in the battery. This electrolyte has the disadvantages of low flash point, poor thermal stability, and being flammable, bringing unpredictable safety risks to the use of the battery, and its application in a wider field is also limited. Therefore, the issue of developing a new type of battery with high energy density, high safety, and high reliability is important and urgent. Developing a cathode material with a high potential for lithium and a high specific capacity is the key point for realizing the high energy density of the battery. For example, the research and development and industrialization of high-voltage lithium cobalt oxide cathode materials, lithium-rich manganese-based cathode materials, and high-nickel ternary cathode materials are accelerating. However, the measure for realizing the high safety of the battery is to solidify the battery and use a highly safe solid electrolyte instead of the liquid electrolyte of the conventional lithium battery. However, in terms of lithium-rich oxide cathode materials with a high specific capacity, for example, for Li2MnO3, the theoretical capacity is 458 mAh / g, for Li2NiO2, the theoretical capacity is 513 mAh / g, and for Li5FeO4, the theoretical capacity is 867 mAh / g. However, all of these materials have the problems of low initial efficiency and poor electrochemical reversibility. Therefore, the development of other cathode material systems is highly necessary. For example, metal halide materials have a relatively high voltage platform (>3V) and specific capacity (>400 mAh / g). Especially for metal chloride-based batteries, corresponding battery systems have already achieved initial success. For example, 20 years ago, NASA developed a Li / CuCl2-based secondary battery for use in low-temperature space power. The specific energy of this battery system at -70°C is 52.9 Wh / kg (data source: NASA SBIR Phase I, project name: "Lithium-Copper Chloride Rechargeable Battery for Low Temperature Space Power"). F.W. Dampier et al. used a LiAlCl4SO2 electrolyte in the Li / CuCl2 system, cycled it 200 times in an environment at 23°C, and tested the low-temperature discharge performance at -20°C / -30°C / -40°C / -50°C / -60°C / -70°C respectively. When manufacturing this liquid electrolyte, gaseous SO2 is injected into the mixture of LiCl and AlCl3. When the battery is used at normal temperature and high temperature, high-pressure gas components are generated inside. Therefore, glass and stainless steel materials are adopted for the battery packaging to prevent the internal pressure from becoming excessive and causing safety problems when used at high temperature. Such a battery system has excellent performance, but the battery manufacturing process is complex, the proportion of the packaging material is large, and its energy density is also restricted (F.W. Dampier, et al. Low Temperature Performance of the Rechargeable Lithium-Copper Chloride Battery).Ting Li et al. used AgCl and CuCl2 as cathode materials, and the specific capacities reached 258 mAh / g and 560 mAh / g respectively. However, the battery used a liquid electrolyte and combined soluble CuCl2 with mesoporous carbon CMK-3, but the adverse effect that CuCl2 was dissolved in the electrolyte could not be completely avoided (Ting Li, et al. Electrochimica Acta 68 (2012) 202-205. Transition-metal chlorides as conversion cathode materials for Li-ion batteries).

[0003] Currently, the academic research and industrial application of all-solid-state batteries have received sufficient attention and development. The ionic electrical conductivities of new types of sulfide solid electrolytes and halide solid electrolytes are constantly improving and have thus exceeded that of liquid electrolytes. All-solid-state batteries with different cathode systems are also being developed. For example, Patent CN 116053478 A discloses a cathode material of metal fluoride coated with a carbon layer for all-solid-state batteries. Such a method can improve the electron and electrical conductivity of the metal fluoride material. However, with the change in the volume of the cathode material during the reaction process, the electrical connection of the material gradually becomes ineffective, and the battery performance deteriorates continuously. Patent CN 109546209 A discloses an all-solid-state polymer electrolyte and a rechargeable chloride ion battery. The all-solid-state polymer material capable of conducting chloride ions is an electrolyte, and the composition of this electrolyte includes a polymer matrix, an active chlorine salt, and a solid plasticizer. The cathode material is a metal chloride, a metal chlorate oxide, or a chlorine-doped conductive polymer material. Such chloride ion solid electrolytes have too low ionic electrical conductivity at room temperature, especially at low temperatures, generally below 10 -4 S / cm, and the capacity of the battery active material in such a system is limited, generally below 200 mAh / g. Therefore, it is very necessary to develop a new material system for all-solid-state batteries with high energy density and high safety.

Summary of the Invention

Problems to be Solved by the Invention

[0004] The technical problem to be solved by the present invention is to develop a new solid battery active material and manufacturing process. The present invention provides a solid-state battery-coated halide cathode composite material for solving the above problems, a manufacturing method thereof, and an application. By means of a spray drying method, a composite material composed of a metal halide and a halide solid electrolyte capable of conducting lithium ions is manufactured in one step and has good electrochemical performance.

Means for Solving the Problems

[0005] The present invention is realized by the following technical solutions. A method for manufacturing a solid-state battery-coated halide cathode composite material, dissolving a metal halide and a halide solid electrolyte in deionized water to produce an aqueous metal salt solution; using a spray drying process to spray the obtained aqueous metal salt solution into a high-temperature chamber for drying and granulation, and finally forming a spherical cathode composite material with a metal halide as the inner core and a halide solid electrolyte as the outer layer by utilizing the characteristic that the solute solubilities are different. Here, the solubility of the metal halide is lower than that of the halide solid electrolyte. The present invention provides a metal halide cathode composite material for a solid-state battery. Its inner core is a metal halide active material with a relatively high specific capacity, and the outer layer is a lithium-containing halide electrolyte material that can not only conduct lithium ions but also has an active capacity. This not only improves the ionic and electrical conductivity of the material but also can greatly improve the proportion of the active material, effectively improving the energy density of the battery. In addition, by using a solidified electrolyte instead of the liquid or gaseous components in the conventional electrolyte, not only the problem of dissolution of the halide cathode material in the liquid electrolyte is solved, but also the wide-temperature performance and safety performance of the battery are comprehensively improved. Using the spray drying process, an aqueous metal salt solution obtained is sprayed into a high-temperature chamber by a high-speed and high-pressure inert carrier gas for drying and granulation. Utilizing the characteristic of different solute solubilities, a coated spherical cathode composite material is finally formed, where the inner core is a metal halide, the outer layer is a halide solid electrolyte, and the inner and outer layers are in sufficient contact. When manufacturing the cathode composite, materials with different solubilities are preferentially selected. Generally, the solubility of the metal halide is lower than that of the halide solid electrolyte. During heating and evaporation, the metal halide crystallizes first to form crystal nuclei, and the halide solid electrolyte crystallizes on its surface to form the product with the target structure. In the spray drying process, the inert carrier gas is one of argon gas or nitrogen gas. More selectively, the mass ratio of the metal halide to the halide solid electrolyte is 1:1 - 9:1, and more preferably 3:1 - 7:1. More selectively, the metal halide is used as a cathode active material with the general formula MX n where M includes one of Ni, Fe, Mn, Sb, Cu, Mo, Mg, Bi, Co, Cd, Zn, V, Ag, and X includes one of F, Cl, Br, I. Non-fluoride materials with high abundance of raw materials and low manufacturing costs, such as SbCl3, CuCl2, FeCl2, CuCl, NiCl2, MnCl2, MgCl2, FeCl3, CdCl2, are more preferable. In addition, the bond energy formed by the metal and Cl, Br, I elements is weaker than the bond energy of M-F, and the electron and electrical conductivity of the material is higher. More selectively, the general formula of the halide solid electrolyte is Li m MX n where M includes one of Ni, Fe, Mn, Cr, Co, Zn, Cr, Mg, Ti, V, RE, and X includes one of F, Cl, Br, I. Solid electrolyte materials with low material costs and having reversible electrochemical capacity, such as Li6VCl8, Li2MnCl4, Li2FeCl4, Li3TiCl6, Li2MgCl4, Li2FeBr4, Li2MnBr4, are more preferable. More preferably, for the aqueous metal salt solution, its mass concentration is from 5% to the saturated state. More preferably, the operating temperature of the high-temperature chamber is controlled to be 150°C - 500°C. More preferably, it is 200°C - 300°C. A spherical cathode composite material of an all-solid-state battery-coated halide cathode composite material, wherein the inner core is a metal halide and the outer layer is a halide solid electrolyte, is obtained by being manufactured by the above-mentioned manufacturing method of the all-solid-state battery-coated halide cathode composite material. An all-solid-state battery, wherein the cathode active material is a material obtained by being manufactured by the above-mentioned manufacturing method of the all-solid-state battery-coated halide cathode composite material, or includes the above-mentioned all-solid-state battery-coated halide cathode composite material. Furthermore, optionally, the anode active material includes one of metallic lithium, lithium-based alloys, and non-metallic anode materials. Lithium-based alloys include binary alloys such as lithium beryllium alloy, lithium magnesium alloy, lithium boron alloy, lithium aluminum alloy, lithium indium alloy, lithium gallium alloy, lithium silicon alloy, lithium antimony alloy, lithium tin alloy, lithium zinc alloy, lithium silver alloy, and ternary alloys or multi-component lithium alloys such as lithium beryllium magnesium alloy, lithium boron aluminum alloy, lithium indium gallium alloy, lithium tin antimony alloy. Non-metallic anodes include prelithiated graphite, hard carbon, silicon, and silicon-carbon composites. More preferably, an anode material with low strain in the electrochemical reaction process is selected, such as a lithium-based alloy, prelithiated graphite, or hard carbon. Furthermore, optionally, the solid electrolyte includes one of organic polymer solid electrolytes, inorganic oxide solid electrolytes, sulfide solid electrolytes, halide solid electrolytes, and organic-inorganic composite solid electrolytes. The organic polymer solid electrolyte contains one of polyethylene oxide (PEO), polycarbonate (PPC), polysiloxane (PS), polyvinylidene fluoride (PVDF), polyvinylidene fluoride - hexafluoropropylene (PVDF - HFP), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyacrylic acid (PAA), polyethyl methacrylate (PEMA), polyurethane (PU), polyvinyl chloride (PVC) polymers and their derivatives. The inorganic oxide solid electrolyte contains one of LISICON - type fast ion conductors (LZGO), NASICON - type fast ion conductors (LATP, LAGP), Garnet - type (LLZO, LLZTO), Perovskite - type (LLTO). The sulfide solid electrolyte is an amorphous Li2S - P2S5, Li2S - SiS2, Li2S - GeS2, microcrystalline Li3PS4, Li7P3S 11 , Li2S - P2S5, crystalline Thio - LISICON - type Li2S - GeS2 - P2S5, thiogermanium ore - type Li6PS5X (X: Cl, Br, I), LGPS - type (Li 10 GeP2S 12 ) and contains one of them. The halide solid electrolyte contains one of LiaMX4 - type (M: Mn, Zn; X: Cl, Br, I) such as Li2MnCl4, Li2ZnCl4, etc., LiaMX6 - type (M: Y, In, Zr; X: Cl, Br, I) such as Li3YCl6, Li3InCl6, Li2ZrCl6, etc., LiaMX8 - type (M: Co, V; X: Cl, Br, I) such as Li6CoCl8, Li6VCl8, etc. The organic - inorganic composite solid electrolyte is a composite solid electrolyte of the above - mentioned organic polymer solid electrolyte and inorganic solid electrolytes such as inorganic oxide solid electrolytes, sulfide solid electrolytes, and halide solid electrolytes.

Advantages of the Invention

[0006] The present invention has the following advantages and beneficial effects. The coated metal halide cathode material, its manufacturing method, and application according to the present invention are based on the crystal law of metal salts. Using the spray drying method, a spherical cathode composite material with a metal halide core and a halide solid electrolyte outer layer having a stepwise composition is manufactured in one step. When this composite is applied to an all-solid-state battery, it has significant advantages. Specifically, it has the following several advantages.

[0007] 1. The cathode composite material is a metal halide cathode composite material, which has a relatively high voltage platform, generally higher than 3V, and a relatively high specific capacity, generally greater than 300 mAh / g, higher than conventional cathode materials, and can significantly improve the energy density of the battery.

[0008] 2. The core of the cathode composite material is a metal halide active material, and the outer layer is a lithium-containing halide electrolyte material that can not only conduct lithium ions but also has active capacity. This can not only improve the ionic and electrical conductivity of the material but also significantly improve the proportion of the active material in terms of material composition, which is very advantageous for constructing high-energy density batteries.

[0009] 3. In the manufacture of the cathode composite material, the target product is manufactured in one step from a metal salt solution using the spray drying process, which has the characteristics of a short process flow and a high product yield.

[0010] 4. The cathode composite material has a relatively high ionic and electrical conductivity. When manufacturing the cathode plate, it is not necessary to add a high proportion of solid electrolyte, so the proportion of the cathode active material can be improved at the plate level.

[0011] 5. The solid electrolyte used in the all-solid-state battery not only improves the safety performance and high-temperature performance of the battery but also avoids the dissolution of the halide cathode material in the organic liquid electrolyte, solving the inherent problems of this type of cathode material.

[0012] 6. After being packaged, this type of all-solid-state lithium battery reaches a fully charged state and can be directly discharged and used. In addition, the battery consistency can be determined by the open-circuit voltage and internal resistance, eliminating the need for additional charging and formation processes, significantly shortening the process, and reducing the manufacturing cost of the battery.

Brief Description of the Drawings

[0013]

Figure 1

Figure 2

Figure 3

Figure 4

Embodiments for Carrying Out the Invention

[0014] The drawings described herein are used to provide a further understanding of the embodiments of the present invention, constitute a part of this application, and do not constitute a limitation to the embodiments of the present invention. To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be described in more detail below by combining examples with the drawings. The exemplary embodiments of the present invention and their descriptions are only for interpreting the present invention and do not limit the present invention.

[0015] Example 1 This example provides an all-solid-state battery-coated halide cathode composite material, and the specific manufacturing method is as follows. Step 1: Dissolve CuCl2 and Li2MnCl4 with a mass ratio of 2:1 in deionized water to produce 2 L of an aqueous solution with a mass concentration of 40%. Step 2: The aqueous solution was sent to a small spray dryer using a diaphragm pump for recrystallization and drying processes. The carrier gas was high-purity nitrogen gas, the air supply pressure was 5 MPa, the input amount was 50 mL / min, the hot air temperature at the air inlet was 300 °C, and the hot air temperature at the exhaust outlet was 80 °C. The finally obtained solid particles were 600 g, and the yield was 75%. The structure of the positive electrode composite material was a coated structure, and the surface of the CuCl2 material was coated with a layer of dense Li2MnCl4 solid electrolyte material. It was as shown in Figure 1.

[0016] Example 2 This example provides a coated halide positive electrode composite material for all-solid-state batteries. The specific manufacturing method is as follows. Step 1: VCl3 and Li6VCl8 with a mass ratio of 3:1 were dissolved in deionized water to produce 2 L of an aqueous solution with a mass concentration of 30%. Step 2: The aqueous solution was sent to a small spray dryer using a diaphragm pump for recrystallization and drying processes. The carrier gas was high-purity nitrogen gas, the air supply pressure was 5 MPa, the input amount was 50 mL / min, the hot air temperature at the air inlet was 300 °C, and the hot air temperature at the exhaust outlet was 80 °C. The finally obtained solid particles were 400 g, and the yield was 67%. The structure of the positive electrode composite material was a coated structure, and the surface of the VCl3 material was coated with a layer of dense Li6VCl8 solid electrolyte material. It was as shown in Figure 1.

[0017] Example 3 This example provides a solid-state battery, which is obtained by manufacturing with the coated halide positive electrode composite material according to Example 1. The specific manufacturing method is as follows. Step 1: 200 g of the positive electrode material manufactured in Example 1 was taken, 10% of the Li3InCl6 solid electrolyte material, 2% of CNT, and 1% of PTFE were added, and a positive electrode plate was manufactured by a dry method process using a small rolling mill. The thickness of the electrode plate was 150 μm, and the surface loading was 28 mg / cm 2 It was. Step 2: Take 200 g of silicon-carbon anode material (SiC-800) with a specific capacity of 800 mAh / g, add 20% of Li3InCl6 solid electrolyte material, 2% of CNT, and 1% of PTFE, and use a small rolling mill to manufacture the anode plate by a dry process. Roll a 5-μm-thick ultra-thin lithium foil on the surface for contact diffusion to perform lithium pre-intercalation, and finally manufacture an anode with a lithium-silicon alloy layer on the surface. Step 3: Take 20 g of Li3InCl6 solid electrolyte material, add 1% of PTFE, and manufacture a solid electrolyte membrane by a dry process. The thickness was 60 μm. Step 4: Stack the above anode, electrolyte membrane, and cathode in sequence, then hot press and package to manufacture a pouch cell. The pouch cell is as shown in Figure 4.

[0018] Example 4 This example provides a solid battery, which is manufactured from the coated halide cathode composite material according to Example 2. The specific manufacturing method is as follows. Step 1: Take 200 g of the cathode material manufactured in Example 2, add 10% of Li3InCl6 solid electrolyte material, 2% of CNT, and 1% of PTFE, and use a small rolling mill to manufacture the cathode plate by a dry process. The thickness of the plate is 140 μm, and the areal loading is 25 mg / cm 2 was. Step 2: Take 200 g of silicon-carbon anode material (SiC-800) with a specific capacity of 800 mAh / g, add 20% of Li3InCl6 solid electrolyte material, 2% of CNT, and 1% of PTFE, and use a small rolling mill to manufacture the anode plate by a dry process. Roll a 5-μm-thick ultra-thin lithium foil on the surface for contact diffusion to perform lithium pre-intercalation, and finally manufacture an anode with a lithium-silicon alloy layer on the surface. Step 3: Take 20 g of Li3InCl6 solid electrolyte material, add 1% of PTFE, and manufacture a solid electrolyte membrane by a dry process. The thickness was 60 μm. Step 4: After laminating the above-mentioned negative electrode, electrolyte membrane, and positive electrode in sequence, hot pressing was performed for packaging to manufacture a pouch battery. Example 5 This example provides a solid-state battery, and the specific manufacturing method is as follows. Step 1: To 200 g of the positive electrode in Example 2, 10% of the Li6PS5Cl solid electrolyte material, 2% of CNT, and 1% of PTFE were added, and a positive electrode plate was manufactured by a dry method process using a small rolling mill. The thickness of the electrode plate was 140 μm, and the surface loading was 23 mg / cm 2 was. Step 2: Lithium boron alloy (LiB alloy, lithium content 45%) with a thickness of 80 μm was sliced, and a copper foil was pressed against it to make tabs for use. Step 3: 20 g of the Li6PS5Cl solid electrolyte material was taken, 1% of PTFE was added, and a solid electrolyte membrane was manufactured by a dry method process. The thickness was 60 μm. Step 4: After laminating the above-mentioned negative electrode, electrolyte membrane, and positive electrode in sequence, hot pressing was performed for packaging to manufacture a pouch battery.

[0019] Comparative Example 1 This example provides a positive electrode material, and the specific manufacturing method is as follows. 200 g of a positive electrode material of CuCl2 and Li2MnCl4 with a mass ratio of 2:1 was ball-milled and mixed to obtain a composite positive electrode material. This material was obtained by randomly stacking and combining CuCl2 and Li2MnCl4, as shown in Figure 2.

[0020] Comparative Example 2 This example provides a positive electrode material, and the specific manufacturing method is as follows. Step 1: CuCl2 and Li2MnCl4 with a mass ratio of 2:1 were dissolved in deionized water to prepare 2 L of an aqueous solution with a mass concentration of 40%. Step 2: The solution was vacuum-dried in an oven at 200 °C to obtain a CuCl2 and Li2MnCl4 positive electrode composite material containing crystal water. Step 3: The composite cathode material containing water of crystallization was calcined at 300 °C in an argon gas atmosphere to obtain the final composite cathode material. This material has an incomplete uniform coating structure as shown in Figure 3.

[0021] Comparative Example 3 This example provides a solid-state battery, and the specific manufacturing method is as follows. Step 1: Take 200 g of the cathode material provided in Comparative Example 1, add 10% of the Li3InCl6 solid electrolyte material, 2% of CNT, and 1% of PTFE, and use a small rolling mill to manufacture a cathode plate by a dry process. The thickness of the plate was 165 μm, and the surface loading was 30 mg / cm 2 Thereafter. Step 2: Take 200 g of a silicon-carbon anode material (SiC-800) with a specific capacity of 800 mAh / g, add 20% of the Li3InCl6 solid electrolyte material, 2% of CNT, and 1% of PTFE, and use a small rolling mill to manufacture an anode plate by a dry process. A 5-μm-thick ultra-thin lithium foil was rolled on the surface for contact diffusion to perform lithium pre-intercalation, and finally an anode with a lithium-silicon alloy layer on the surface was manufactured. Step 3: Take 20 g of the Li3InCl6 solid electrolyte material, add 1% of PTFE, and manufacture a solid electrolyte membrane by a dry process. The thickness was 60 μm. Step 4: After laminating the above anode, electrolyte membrane, and cathode in sequence, hot pressing and packaging were performed to manufacture a pouch battery.

[0022] Comparative Example 4 This example provides a solid-state battery, and the specific manufacturing method is as follows. Step 1: Take 200 g of the cathode material provided in Comparative Example 2, add 10% of the Li3InCl6 solid electrolyte material, 2% of CNT, and 1% of PTFE, and use a small rolling mill to manufacture a cathode plate by a dry process. The thickness of the plate was 165 μm, and the surface loading was 30 mg / cm 2 Thereafter. Step 2: Take 200 g of silicon-carbon anode material (SiC-800) with a specific capacity of 800 mAh / g, add 20% of Li3InCl6 solid electrolyte material, 2% of CNT, and 1% of PTFE, and use a small rolling mill to manufacture the anode plate by a dry process. Roll a 5-μm-thick ultra-thin lithium foil on the surface for contact diffusion to perform lithium pre-intercalation, and finally manufacture an anode with a lithium-silicon alloy layer on the surface. Step 3: Take 20 g of Li3InCl6 solid electrolyte material, add 1% of PTFE, and manufacture a solid electrolyte membrane by a dry process. The thickness was 60 μm. Step 4: Stack the above anode, electrolyte membrane, and cathode in sequence, then hot press and package them to manufacture a pouch battery.

[0023] Comparative Example 5 This example provides a solid-state battery, and the specific manufacturing method is as follows. Step 1: Take 200 g of CuCl2 cathode material, add 10% of Li3InCl6 solid electrolyte material, 2% of CNT, and 1% of PTFE, and use a small rolling mill to manufacture the cathode plate by a dry process. The thickness of the plate was 165 μm, and the surface loading was 30 mg / cm 2 It was. Step 2: Take 200 g of silicon-carbon anode material (SiC-800) with a specific capacity of 800 mAh / g, add 20% of Li3InCl6 solid electrolyte material, 2% of CNT, and 1% of PTFE, and use a small rolling mill to manufacture the anode plate by a dry process. Roll a 5-μm-thick ultra-thin lithium foil on the surface for contact diffusion to perform lithium pre-intercalation, and finally manufacture an anode with a lithium-silicon alloy layer on the surface. Step 3: Take 20 g of Li3InCl6 solid electrolyte material, add 1% of PTFE, and manufacture a solid electrolyte membrane by a dry process. The thickness was 60 μm. Step 4: Stack the above anode, electrolyte membrane, and cathode in sequence, then hot press and package them to manufacture a pouch battery.

[0024] Comparative Example 6 This example provides a solid-state battery, and the specific manufacturing method is as follows. Step 1: Take 200 g of VCl3 cathode material, add 10% of Li3InCl6 solid electrolyte material, 2% of CNT, and 1% of PTFE, and use a small rolling mill to manufacture a cathode plate by a dry process. The thickness of the plate is 140 μm, and the surface loading is 24 mg / cm 2 was. Step 2: Take 200 g of silicon-carbon anode material (SiC-800) with a specific capacity of 800 mAh / g, add 20% of Li3InCl6 solid electrolyte material, 2% of CNT, and 1% of PTFE, and use a small rolling mill to manufacture an anode plate by a dry process. Roll a 5-μm-thick ultra-thin lithium foil on the surface for contact diffusion to perform lithium pre-intercalation, and finally manufacture an anode with a lithium-silicon alloy layer on the surface. Step 3: Take 20 g of Li3InCl6 solid electrolyte material, add 1% of PTFE, and manufacture a solid electrolyte membrane by a dry process. The thickness was 60 μm. Step 4: Stack the above anode, electrolyte membrane, and cathode in sequence, then hot press and package to manufacture a pouch battery.

[0025] Comparative Example 7 This example provides a solid-state battery, and the specific manufacturing method is as follows. Stack the above lithium-boron alloy anode, Li6PS5Cl electrolyte membrane, and the cathode in Comparative Example 6 in sequence, then hot press and package to manufacture a pouch battery. I. Performance Test 1. Test method: (1) Ionic conductivity: Press the cathode composite material into a wafer with a diameter of 10 mm, assemble a stainless steel / cathode composite material / stainless steel mold battery, and use an electrochemical station to test the AC impedance of the mold battery. The test temperature is 25 °C, and the calculation formula for ionic conductivity is σ = L / (R.S), where L is the thickness of the electrolyte membrane, S is the area of the electrolyte membrane, and R is the electrolyte membrane impedance measured by the AC impedance method. (2) Performance of the pouch solid-state battery: Using a charge-discharge test machine, the assembled pouch battery was tested for its high-temperature, normal-temperature, and low-temperature performance at 0.2C at different temperatures of 80°C / 25°C / -40°C respectively, and the test voltage range was 2.0V - 3.8V. 2. Test Results (1) The test results of the ionic and electrical conductivity of the positive electrode composite material are as shown in Table 1. Table 1 Ionic and Electrical Conductivity of Positive Electrode Composite Materials According to Examples 1-2 and Comparative Examples 1-2 JPEG0007714091000001.jpg87155 (2) The test results of the performance of the pouch solid-state battery are as shown in Table 2. Table 2 Discharge Specific Capacity of Solid-State Batteries According to Examples 3-5 and Comparative Examples 3-7 The embodiments for carrying out the invention described above further elaborate on the object, technical solution, and beneficial effects of the present invention. However, it should be understood that what is described above is merely the embodiments for carrying out the invention of the present invention and is not intended to limit the protection scope of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should all be included within the protection scope of the present invention.

Explanation of Reference Signs

[0026] The light-colored region represents the solid halide electrolyte, and the dark-colored region represents the halide positive electrode material.

Claims

1. A method for manufacturing a solid-state battery-coated halide cathode composite material, comprising: dissolving a metal halide and a halide solid electrolyte in deionized water to produce an aqueous metal salt solution; using a spray drying process to spray the obtained aqueous metal salt solution into a high-temperature chamber for drying and granulation, and finally forming a spherical cathode composite material with a metal halide core and a halide solid electrolyte outer layer by utilizing the characteristic of different solute solubilities; wherein the solubility of the metal halide is lower than that of the halide solid electrolyte; The metal halide, as a cathode active material, has a general formula of MX ｎ and is Here, MX ｎ In this case, M in MX contains one of Ni, Fe, Mn, Sb, Cu, Mo, Mg, Bi, Co, Cd, Zn, V, Ag, and X in MX ｎ contains one of F, Cl, Br, I. The general formula of the halide solid electrolyte is Li ｍ MX ｎ and is Here, Li ｍ MX ｎ In, M includes one of Ni, Fe, Mn, Cr, Co, Zn, Mg, Ti, V, Re, and Li ｍ MX ｎ In, X includes one of F, Cl, Br, I, and a method for manufacturing an all-solid-state battery-coated halide cathode composite material is characterized by this.

2. The method for manufacturing a solid-state battery-coated halide cathode composite material according to Claim 1, characterized in that the mass ratio of the metal halide to the halide solid electrolyte is 1:1 - 9:

1.

3. The method for manufacturing a solid-state battery-coated halide cathode composite material according to Claim 1, characterized in that the mass concentration of the aqueous metal salt solution is from 5% to saturation.

4. The method for manufacturing a solid-state battery-coated halide cathode composite material according to Claim 1, characterized in that the operating temperature of the high-temperature chamber is controlled at 150°C - 500°C.

5. A method for manufacturing a solid-state battery, characterized by using a cathode active material comprising the solid-state battery-coated halide cathode composite material according to any one of Claims 1 to 4.

6. The method for manufacturing a solid-state battery according to Claim 5, characterized by using an anode active material comprising any one of metallic lithium, lithium-based alloys, and non-metallic anode materials.

7. The method for manufacturing a solid-state battery according to Claim 6, characterized by using a solid electrolyte comprising any one of organic polymer solid electrolytes, inorganic oxide solid electrolytes, sulfide solid electrolytes, halide solid electrolytes, and organic-inorganic composite solid electrolytes. ​ ​ ​

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