A negative electrode material for a solid-state battery, its preparation method and application

Abstract

The present invention belongs to the field of battery technology, and specifically relates to a solid-state battery negative electrode material, a preparation method thereof, and an application thereof. The solid-state battery negative electrode material is a silver-based MOFs-derived carbon material, and its preparation method comprises: (1) dissolving a silver salt and an organic ligand in a solvent for a solvothermal reaction, continuously stirring during the reaction, and purifying to obtain a silver-based MOFs material after the reaction; (2) drying the silver-based MOFs material to remove the solvent in the pores; (3) placing the silver-based MOFs material treated in step (2) in a high-temperature furnace, slowly heating it to 600-800°C under an inert gas atmosphere for pyrolysis, and cooling to obtain a silver-based MOFs-derived carbon material. In the negative electrode material, silver particles are uniformly dispersed in the carbon material to suppress lithium dendrites, without the need to add a solid electrolyte, thereby improving energy density; MOFs serve as the negative electrode skeleton, greatly reducing macroscopic volume expansion and contraction during lithium deposition and desorption, thereby solving the lifespan problem.

Description

Technical Field

[0001] The present invention belongs to the technical field of batteries, and in particular relates to a solid-state battery negative electrode material and a preparation method thereof, as well as a battery using the material. Background Art

[0002] Negative electrode materials are key materials for lithium-ion batteries. During charging, lithium ions migrate through the electrolyte and are embedded in the negative electrode material for storage. During discharge, lithium ions are released from the negative electrode and return to the positive electrode, where they power the device through the flow of electrons in the external circuit. Negative electrode materials are a key determinant of battery performance and require a balance between capacity, stability, and conductivity. In all-solid-state batteries, in particular, negative electrode materials are closely related to electrical performance and play a decisive role in key performance factors such as energy density, cycle stability, and safety. In the emerging field of all-solid-state batteries, the performance of negative electrode materials has become a key bottleneck restricting their commercial application. A precise balance must be achieved between ion transmission efficiency, volume deformation control, and interface stability to meet the stringent requirements of high-energy-density application scenarios.

[0003] In existing technologies, the development of negative electrode materials faces the following technical bottlenecks and challenges:

[0004] Graphite, the mainstream commercial anode material, offers advantages such as low cost and low volume expansion (approximately 10%) after lithium insertion. However, its theoretical specific capacity is only 372 mAh / g, severely limiting the battery's energy density. In all-solid-state batteries, the graphite anode requires the addition of a solid electrolyte to ensure ionic conductivity, further reducing its volumetric energy density and making it difficult to meet the demands of high-energy-density applications.

[0005] Lithium metal materials have a high specific capacity, with a theoretical specific capacity of 3860mAh / g, and can be used directly as a lithium source. However, repeated deposition / dissolution of lithium causes the electrode to expand and contract, destroying the structure and reducing the cycle life. After the lithium metal completely leaves the negative electrode, the volume of the negative electrode side changes greatly, and it cannot be deposited evenly after returning, thus forming dendrites, which may pierce the diaphragm and cause a short circuit, posing a safety hazard. Lithium metal is soft and easily deformed. In an all-solid-state battery, it may deform once it is subjected to pressure, resulting in uneven lithium insertion. Especially under high pressure (isostatic pressing or during cycling), the lithium metal electrode is deformed by rolling, affecting the NP ratio, resulting in deviation from the design and causing failure.

[0006] To alleviate the volume expansion problem, CN118763172A in situ composites the active material nanosilicon with MOF-derived carbon and utilizes carbon nanotubes to form a three-dimensional conductive network. However, nanosilicon and carbon nanotubes tend to agglomerate in solvents, resulting in poor ultrasonic dispersion uniformity. Furthermore, the pre-added nanomaterials interfere with the uniform formation of the MOF skeleton, introducing structural defects. This type of silicon-carbon composite still requires the addition of an electrolyte, making it suitable only for conventional lithium-ion batteries and not for direct application in solid-state battery systems.

[0007] To address the problem of lithium dendrites, CN118763172A mixes a pretreated three-dimensional porous framework with a metal-organic framework (MOF) material; carbonizes the mixture in a muffle furnace; and then infuses the entire framework with molten liquid lithium metal to create a novel three-dimensional metallic lithium anode. This process relies on growing metal oxides on a metal foam substrate, which is complex and costly. Furthermore, the large-pore framework is prone to collapse and deformation under stress, limiting its practicality in all-solid-state batteries.

[0008] Existing all-solid-state battery negative electrode materials generally have inherent defects: once the current density is uneven or the interface changes, lithium ions are very likely to deposit on the electrode surface, causing lithium dendrite growth, and ultimately leading to deterioration of life or short circuit.

[0009] To address this inherent defect, Ag / C composite materials use a composite structure in which silver nanoparticles are dispersed in a porous carbon matrix, using silver to induce uniform lithium deposition and reduce the risk of dendrite penetration. At the same time, lithium ions can be deposited into the porous carbon structure, and the specific capacity can reach 500-900mAh / g. However, this solution also has disadvantages. When mechanical stirring or high-energy ball milling is used to disperse silver nanoparticles in the porous carbon, the silver nanoparticles easily agglomerate and the dispersion effect is not good. Therefore, it is very easy to cause the effect of inducing uniform lithium ion deposition in some areas, resulting in lithium precipitation. In addition, the dispersion of silver particles is highly random and cannot be designed in a targeted manner, which further limits its performance optimization and application potential.

[0010] In summary, the development of anode materials for all-solid-state batteries urgently requires addressing the uniform dispersion of silver particles in carbon materials, while simultaneously meeting stringent requirements such as rapid ion transport, controllable volume deformation, and interfacial stability. Promoting the development of anode materials towards higher energy density, longer lifespan, and faster charging through material innovation and structural design is not only key to improving lithium-ion battery performance but also a significant driver of technological innovation in areas such as electric vehicles and energy storage systems. Therefore, exploring new anode materials or improving the dispersion technology of existing materials to maximize energy density has become a hot topic and a frontier of current research. Summary of the Invention

[0011] The present invention aims to provide a negative electrode material with a novel structural design, which can solve the problem of poor dispersion uniformity of silver particles in carbon materials.

[0012] To achieve the above objectives, the present invention provides the following technical solutions:

[0013] A method for preparing a solid-state battery negative electrode material, wherein the solid-state battery negative electrode material is a silver-based MOFs-derived carbon material, and the preparation method comprises the following steps:

[0014] (1) dissolving silver salt and organic ligand in a solvent for solvothermal reaction, stirring continuously during the reaction, and purifying to obtain silver-based MOFs material after the reaction is completed;

[0015] (2) drying the silver-based MOFs material to remove the solvent in the pores;

[0016] (3) placing the silver-based MOFs material treated in step (2) in a high-temperature furnace, slowly heating it to 600-800° C. under an inert gas atmosphere for pyrolysis, and cooling it to obtain a silver-based MOFs-derived carbon material;

[0017] The molar ratio of the silver salt to the organic ligand in step (1) is (1:1)-(3:1), and the stirring conditions are: stirring at 200-400 rpm for 6-18 hours, then stirring at 50-150 rpm for 4-10 hours, and then stirring at 5-40 rpm for 4-16 hours.

[0018] When the pyrolysis temperature exceeds 800°C, the MOFs-derived carbon framework is prone to irreversible collapse due to a significant decrease in structural stability, resulting in a serious decline in electrode cycle performance. When it exceeds 900°C, Ag volatilizes, causing the derived carbon to lose the ability to induce uniform deposition of lithium ions. When the temperature is lower than 600°C, it is not enough to drive the effective carbonization process of the MOFs material, indicating that the pyrolysis temperature needs to be precisely controlled in a moderate range to simultaneously achieve structural integrity and carbonization effect.

[0019] Optionally, the silver salt is selected from at least one of silver nitrate, silver acetate, silver chloride or silver carbonate.

[0020] Optionally, the solvent is selected from N,N-dimethylformamide (DMF), water or ethanol, or a mixture of two or more thereof.

[0021] Optionally, the organic ligand is an organic compound containing multiple coordination sites. Preferably, the organic ligand is selected from polycarboxylic acid compounds, hydroxyl-substituted polycarboxylic acid compounds, imidazole compounds or tetrazole compounds.

[0022] By controlling the ratio of silver salt and organic ligand, the loading amount of Ag in silver-based MOFs-derived carbon materials can be effectively controlled.

[0023] During specific implementation, the desired silver salt, organic ligand, and solvent can be selected based on the specific silver-based MOFs material to be prepared. For example, if the organic ligand is trimesic acid and the silver-based MOFs material prepared is an Ag-BTC material, when the molar ratio of AgNO3 to H3BTC is adjusted from 1:1 to 2:1, the Ag loading amount increases significantly, and more Ag nanoclusters appear in the MOFs framework. When the silver-based MOFs material to be prepared is an Ag-MOF-74 material, the organic ligand can be selected from 2,5-dihydroxyterephthalic acid. When the silver-based MOFs material to be prepared is an Ag-ZIF material, the organic ligand is generally selected from imidazole compounds, such as 2-methylimidazole and benzimidazole. When the silver-based MOFs material to be prepared is an Ag-TAZ material, the organic ligand is generally selected from tetrazole compounds, such as 5-aminotetrazole and 5-methyltetrazole.

[0024] Preferably, the temperature of the solvent thermal reaction is 80-120° C., and the reaction time is 14-44 hours.

[0025] Preferably, in step (2), the drying treatment is vacuum drying, the vacuum drying temperature is 50-120° C., and the drying time is 6-24 hours.

[0026] Optionally, the inert gas is selected from at least one of argon, nitrogen or helium.

[0027] Preferably, the rate of slowly heating is 2-10°C / min.

[0028] Specifically, a method for preparing a solid-state battery negative electrode material comprises the following steps:

[0029] (1) AgNO3 and an organic ligand H3BTC (pyromellitic acid) are dissolved in water and heated to 80–120°C in a closed reactor for 14–44 hours with continuous stirring. After the reaction, the Ag-BTC (silver benzene trimellitic acid) material is obtained by cooling, filtering, washing, and drying.

[0030] The molar ratio of AgNO3 to the organic ligand is (1:1)-(3:1), and the stirring conditions are: stirring at 200-400 rpm for 6-18 hours, then stirring at 50-150 rpm for 4-10 hours, and then stirring at 5-40 rpm for 4-16 hours;

[0031] (2) vacuum drying the Ag-BTC material (drying temperature 50-120°C, drying time 6-24 hours) to remove the solvent in the pores;

[0032] (3) Place the Ag-BTC material treated in step (2) in a tube furnace, introduce Ar or N2 (flow rate 50–100 mL / min) into the tube furnace to exclude oxygen;

[0033] In an inert gas atmosphere, the temperature is slowly increased to 600-800°C at a heating rate of 2-10°C / min for pyrolysis, and the silver-based MOFs-derived carbon material is obtained after natural cooling.

[0034] The present invention also provides a battery, comprising the solid-state battery negative electrode material prepared by the above-described method.

[0035] The silver-based MOFs-derived carbon material prepared by the method of the present invention utilizes the manufacturing characteristics of silver-based MOFs, and silver can be evenly distributed in the material at the atomic level; after the MOFs material is carbonized, the skeleton can provide abundant lithium storage sites as a negative electrode lithium storage material, and silver plays a role in inducing lithium deposition.

[0036] Compared with the prior art, the negative electrode material of the present invention has the following advantages:

[0037] This invention combines the porous properties of MOFs with the structural design of Ag / C composite materials, simultaneously addressing volume expansion and nanosilver dispersion issues, representing a significant breakthrough in the innovation of anode materials for all-solid-state batteries. Silver particles are evenly dispersed within the carbon material, and the placement of the Ag particles can be customized, ensuring overall uniformity and excellent conductivity. This design induces uniform lithium deposition during the manufacture of the battery's anode, addressing the problem of lithium dendrites, a common problem with existing anode materials. It also eliminates the need for solid-state electrolytes, improving energy density. Using this structure as the anode skeleton significantly reduces macroscopic volume expansion and contraction during lithium deposition and removal, addressing battery life concerns. DETAILED DESCRIPTION

[0038] In order to enable those skilled in the art to better understand the technical solutions in this application, the present invention will be further described below in conjunction with specific embodiments. Obviously, the embodiments described are only part of the embodiments of this application, rather than all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without making creative work should fall within the scope of protection of this application. The relevant descriptions of parts and proportions in this specification, unless otherwise specified, are all by weight.

[0039] Example 1

[0040] A method for preparing a silver-based MOFs-derived carbon material comprises the following steps:

[0041] (1) AgNO3 and an organic ligand H3BTC (pyromellitic acid) in a molar ratio of 3:1 were dissolved in water and heated to 100°C in a closed reactor for 24 hours. Stirring was continued during the reaction: first at 250 rpm for 12 hours, then at 100 rpm for 6 hours, and then at 25 rpm for 6 hours. After the reaction, the mixture was cooled, filtered, washed, and dried to obtain Ag-BTC (silver benzene trimellitic acid) material.

[0042] (2) The Ag-BTC material was vacuum dried (drying temperature 60°C, drying time 12 hours) to remove the solvent in the pores;

[0043] (3) The Ag-BTC material treated in step (2) was placed in a tube furnace, and N2 (flow rate 60 mL / min) was introduced into the tube furnace to exclude oxygen; the temperature was slowly increased to 600°C at a heating rate of 5°C / min in a N2 gas atmosphere for pyrolysis, and the silver-based MOFs-derived carbon material was obtained after natural cooling.

[0044] Example 2

[0045] All-solid-state lithium-ion battery preparation process (dry process):

[0046] 1. Preparation of positive electrode sheet: Based on 100 parts of the positive electrode formula, 80 parts of lithium nickel cobalt manganese oxide (NCM811), 3 parts of conductive carbon black (Super-P), 2 parts of polytetrafluoroethylene (PTFE) and 15 parts of Li6PS5Cl solid electrolyte are mixed evenly, and then coated on the surface of the aluminum foil current collector after forming a film through the dry electrode process, and then punched into a positive electrode sheet.

[0047] 2. Preparation of negative electrode sheet: Silver-based MOFs-derived carbon material pyrolyzed at 600°C (i.e., the silver-based MOFs-derived carbon material prepared in Example 1) was used as the negative electrode active material. Based on 100 parts of the negative electrode formula, 97 parts of the silver-based MOFs-derived carbon material, 1 part of conductive carbon black (Super-P), and 2 parts of PTFE were evenly mixed. After forming a film through a dry electrode process, the film was hot-pressed onto the surface of a copper foil current collector and punched into a negative electrode sheet.

[0048] 3. Preparation of solid electrolyte membrane: After 98 parts of Li6PS5Cl and 2 parts of PTFE are mixed evenly, the mixture is formed into a thin film by dry rolling and then punched to obtain a solid electrolyte membrane.

[0049] 4. Battery Assembly: The positive electrode sheet, solid electrolyte membrane, and negative electrode sheet are stacked sequentially in a sandwich structure, creating a stack consisting of 39 positive electrode sheets and 40 negative electrode sheets, ensuring close contact between the layers. The stack is then placed in a battery casing, vacuum-sealed, and further compacted using an isostatic pressing process to create an all-solid-state lithium-ion battery.

[0050] Example 3

[0051] The preparation process for the all-solid-state lithium-ion battery is the same as in Example 2, except that this example uses a silver-based MOFs-derived carbon material pyrolyzed at 800°C as the negative electrode active material. The preparation process for the silver-based MOFs-derived carbon material pyrolyzed at 800°C is the same as in Example 1, except that the pyrolysis temperature is 800°C.

[0052] Example 4

[0053] A method for preparing a silver-based MOFs-derived carbon material comprises the following steps:

[0054] (1) AgNO3 and an organic ligand H3BTC (pyromellitic acid) in a molar ratio of 1:1 were dissolved in water and heated to 120°C in a closed reactor for 14 hours. Stirring was continued during the reaction: first at 400 rpm for 6 hours, then at 150 rpm for 4 hours, and then at 40 rpm for 4 hours. After the reaction, the mixture was cooled, filtered, washed, and dried to obtain the Ag-BTC (pyromellitic acid silver) material.

[0055] (2) The Ag-BTC material was vacuum dried (drying temperature 60°C, drying time 12 hours) to remove the solvent in the pores;

[0056] (3) The Ag-BTC material treated in step (2) was placed in a tube furnace, and N2 (flow rate 60 mL / min) was introduced into the tube furnace to exclude oxygen; the temperature was slowly increased to 600°C at a heating rate of 5°C / min in a N2 gas atmosphere for pyrolysis, and the silver-based MOFs-derived carbon material was obtained after natural cooling.

[0057] The silver-based MOFs-derived carbon material prepared above was used as the negative electrode active material, and the preparation process of the all-solid-state lithium-ion battery was the same as in Example 2.

[0058] Example 5

[0059] A method for preparing a silver-based MOFs-derived carbon material comprises the following steps:

[0060] (1) AgNO3 and an organic ligand H3BTC (pyromellitic acid) in a molar ratio of 1:1 were dissolved in water and heated to 80°C in a closed reactor for 44 hours. Stirring was continued during the reaction: first at 200 rpm for 18 hours, then at 50 rpm for 10 hours, and then at 5 rpm for 16 hours. After the reaction, the mixture was cooled, filtered, washed, and dried to obtain Ag-BTC (silver benzene trimellitic acid) material.

[0061] (2) The Ag-BTC material was vacuum dried (drying temperature 60°C, drying time 12 hours) to remove the solvent in the pores;

[0062] (3) The Ag-BTC material treated in step (2) was placed in a tube furnace, and N2 (flow rate 60 mL / min) was introduced into the tube furnace to exclude oxygen; the temperature was slowly increased to 600°C at a heating rate of 5°C / min in a N2 gas atmosphere for pyrolysis, and the silver-based MOFs-derived carbon material was obtained after natural cooling.

[0063] The silver-based MOFs-derived carbon material prepared above was used as the negative electrode active material, and the preparation process of the all-solid-state lithium-ion battery was the same as in Example 2.

[0064] Comparative Example 1

[0065] The preparation process of the all-solid-state lithium-ion battery is the same as that of Example 2, except that the negative electrode formula of this comparative example only contains graphite, and graphite is used as the negative electrode active material.

[0066] Comparative Example 2

[0067] The preparation process of the all-solid-state lithium-ion battery is the same as that of Example 2, except that graphite is used as the negative electrode active material in this comparative example. Based on 100 parts of the negative electrode formula, there are 87 parts of graphite, 10 parts of Li6PS5Cl solid electrolyte, 1 part of conductive agent Super-P, and 2 parts of PTFE.

[0068] Comparative Example 3

[0069] The preparation process of the all-solid-state lithium-ion battery is the same as that of Example 2, except that the negative electrode formulation of this comparative example contains only lithium metal, and lithium metal is used as the negative electrode active material.

[0070] Comparative Example 4

[0071] The preparation process is the same as that of Example 2, except that this comparative example uses Ag / C as the negative electrode active material. Based on 100 parts of the negative electrode formula, there are 97 parts of Ag / C, 1 part of the conductive agent Super-P, and 2 parts of PTFE.

[0072] Comparative Example 5

[0073] The preparation process for the all-solid-state lithium-ion battery was the same as in Example 2, except that this example used a silver-based MOFs-derived carbon material treated at 1000°C as the negative electrode active material. The preparation process for the silver-based MOFs-derived carbon material pyrolyzed at 1000°C was the same as in Example 1, except that the pyrolysis temperature was 1000°C.

[0074] Comparative Example 6

[0075] A method for preparing a silver-based MOFs-derived carbon material comprises the following steps:

[0076] (1) AgNO3 and an organic ligand H3BTC (pyromellitic acid) in a molar ratio of 3:1 were dissolved in water, heated to 100°C in a closed reactor for 24 hours, and stirred at 25 rpm during the reaction. After the reaction, the mixture was cooled, filtered, washed, and dried to obtain Ag-BTC (silver benzene trimellitic acid) material.

[0077] (2) The Ag-BTC material was vacuum dried (drying temperature 60°C, drying time 12 hours) to remove the solvent in the pores;

[0078] (3) The Ag-BTC material treated in step (2) was placed in a tube furnace, and N2 (flow rate 60 mL / min) was introduced into the tube furnace to exclude oxygen; the temperature was slowly increased to 600°C at a heating rate of 5°C / min in a N2 gas atmosphere for pyrolysis, and the silver-based MOFs-derived carbon material was obtained after natural cooling.

[0079] The silver-based MOFs-derived carbon material prepared above was used as the negative electrode active material, and the preparation process of the all-solid-state lithium-ion battery was the same as in Example 2.

[0080] Comparative Example 7

[0081] A method for preparing a silver-based MOFs-derived carbon material comprises the following steps:

[0082] (1) AgNO3 and organic ligand H3BTC (pyromellitic acid) were dissolved in water at a molar ratio of 3:1, and the mixture was heated to 100°C in a closed reactor for 24 hours with continuous stirring at 500 rpm. After the reaction, the mixture was cooled, filtered, washed, and dried to obtain Ag-BTC (silver benzene trimellitic acid) material.

[0083] (2) The Ag-BTC material was vacuum dried (drying temperature 60°C, drying time 12 hours) to remove the solvent in the pores;

[0084] (3) The Ag-BTC material treated in step (2) was placed in a tube furnace, and N2 (flow rate 60 mL / min) was introduced into the tube furnace to exclude oxygen; the temperature was slowly increased to 600°C at a heating rate of 5°C / min in a N2 gas atmosphere for pyrolysis, and the silver-based MOFs-derived carbon material was obtained after natural cooling.

[0085] The silver-based MOFs-derived carbon material prepared above was used as the negative electrode active material, and the preparation process of the all-solid-state lithium-ion battery was the same as in Example 2.

[0086] The performance of the all-solid-state lithium-ion batteries prepared in the examples and comparative examples is shown in Table 1.

[0087] Table 1

[0088]

[0089] When the battery is cycled at a rate of 1C and the capacity retention rate decays from the initial 100% SOH to 80% SOH, the number of cycles experienced is the cycle life. It can be seen from the results in Table 1 that the energy density and life of the battery are significantly optimized by using the silver-based MOFs-derived carbon material prepared by the present invention as the negative electrode active material. The higher the pyrolysis temperature of the silver-based MOFs-derived carbon material, the higher the porosity and the stronger the lithium storage capacity, which leads to a higher energy density. However, when the pyrolysis temperature exceeds 800°C, the MOFs-derived carbon framework is prone to irreversible collapse due to a significant decrease in structural stability, resulting in a serious decline in the electrode cycle performance. When the pyrolysis temperature exceeds 900°C (for example, 1000°C in Comparative Example 5), Ag volatilizes, causing the derived carbon to lose the ability to induce uniform deposition of lithium ions. There is no solid electrolyte in the negative electrode, and lithium ions cannot be transmitted, so the capacity is lost. In Comparative Example 6, the Ag dispersion is uneven due to the continuous low stirring speed, and Ag is missing or insufficient in some areas, resulting in a significant decrease in energy density and cycle life. In Comparative Example 7, although the Ag dispersion is improved by increasing the stirring speed, the crystal nucleus growth process is inhibited, and an effective continuous skeleton structure cannot be constructed, which results in a significant decrease in energy density.

Claims

1. A method for preparing a solid-state battery negative electrode material, characterized in that: The solid-state battery negative electrode material is a silver-based MOFs-derived carbon material, and the preparation method comprises the following steps: (1) dissolving silver salt and organic ligand in a solvent for solvothermal reaction, stirring continuously during the reaction, and purifying to obtain silver-based MOFs material after the reaction is completed; (2) drying the silver-based MOFs material to remove the solvent in the pores; (3) placing the silver-based MOFs material treated in step (2) in a high-temperature furnace, slowly heating it to 600-800° C. under an inert gas atmosphere for pyrolysis, and cooling it to obtain a silver-based MOFs-derived carbon material; The molar ratio of the silver salt to the organic ligand in step (1) is (1:1)-(3:1), and the stirring conditions are: stirring at 200-400 rpm for 6-18 hours, then stirring at 50-150 rpm for 4-10 hours, and then stirring at 5-40 rpm for 4-16 hours.

2. The preparation method according to claim 1, characterized in that The silver salt is selected from at least one of silver nitrate, silver acetate, silver chloride or silver carbonate.

3. The preparation method according to claim 1, characterized in that The solvent is selected from N,N-dimethylformamide, water or ethanol, or a mixture of two or more thereof.

4. The preparation method according to claim 1, characterized in that The organic ligand is an organic compound containing multiple coordination sites.

5. The preparation method according to claim 4, characterized in that The organic ligand is selected from polycarboxylic acid compounds, hydroxyl-substituted polycarboxylic acids, imidazole compounds or tetrazole compounds.

6. The preparation method according to claim 4, characterized in that The organic ligand is trimesic acid, 2,5-dihydroxyterephthalic acid, 2-methylimidazole, benzimidazole, 5-aminotetrazole or 5-methyltetrazole.

7. The preparation method according to claim 1, characterized in that The temperature of the solvent thermal reaction is 80-120° C., and the reaction time is 14-44 hours.

8. The preparation method according to claim 1, characterized in that The rate of the slow heating is 2-10°C / min.

9. A solid-state battery negative electrode material, characterized in that: The method according to any one of claims 1 to 8 is used for preparation.

10. A battery, characterized in that: Including the solid-state battery negative electrode material as claimed in claim 9.

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