Sulfide solid electrolyte and preparation method and application thereof

Abstract

The invention relates to the field of batteries, in particular to sulfide solid electrolyte as well as a preparation method and application thereof. The preparation method of the sulfide solid electrolyte comprises the following steps: (a) uniformly mixing a sulfide electrolyte and an inert solvent to obtain slurry; and (b) adding a grinding medium and fluorochloromethane into the slurry, and carrying out acoustic resonance treatment and post-treatment to obtain the sulfide solid electrolyte. According to the preparation method of the sulfide solid electrolyte, the technical problems of complex process, low efficiency, interface side reaction, solvent residue and the like caused by step-by-step nanocrystallization and surface modification in the traditional technology are successfully solved, and high-efficiency and low-consumption preparation of the high-performance sulfide solid electrolyte under mild conditions is realized.

Description

Technical Field

[0001] This invention relates to the field of batteries, and more specifically, to a sulfide solid electrolyte, its preparation method, and its application. Background Technology

[0002] Sulfide solid electrolytes (such as Li6PS5Cl) are considered core materials for all-solid-state batteries due to their ultra-high ionic conductivity, but their practical application is constrained by two major challenges: poor interfacial chemical stability and difficulties in nanoscale processing. Current technologies struggle to address both issues simultaneously without compromising the material's intrinsic properties. While wet milling can achieve some nanoscale formation, residual solvents that are difficult to remove completely severely block ion migration channels, leading to a significant decrease in ionic conductivity. Dry mechanical milling, due to the inherent soft and sticky nature of sulfide materials, easily causes cold welding and severe agglomeration of particles, making it impossible to efficiently obtain submicron-sized powders, and it also consumes extremely high energy. Surface coating technologies (such as oxide coatings) used to improve interfacial stability often require high-temperature heat treatment, which can easily trigger harmful interfacial side reactions; while advanced processes such as vapor deposition are expensive and complex, making them difficult to meet the demands of large-scale mass production. Therefore, developing an efficient and low-energy-consumption method that can simultaneously achieve electrolyte nanoscale formation and surface stabilization under mild conditions has become a key technological bottleneck urgently needing to be overcome to promote the industrialization of sulfide all-solid-state batteries.

[0003] In view of this, the present invention is hereby proposed. Summary of the Invention

[0004] This invention aims to overcome the core technical bottleneck of sulfide solid electrolytes, which are difficult to balance ultra-fine nano-scale and high interfacial stability, and provides a sulfide solid electrolyte, its preparation method, and its application.

[0005] In order to achieve the above-mentioned objectives of the present invention, the following technical solution is adopted: One aspect of the present invention relates to a method for preparing a sulfide solid electrolyte, comprising the following steps: (a) The sulfide electrolyte and the inert solvent are mixed to obtain a slurry; (b) After adding grinding media and chlorofluoromethane to the slurry, acoustic resonance treatment and post-treatment are performed to obtain the sulfide solid electrolyte.

[0006] The method for preparing sulfide solid electrolytes successfully solves the technical problems of complex processes, low efficiency, interfacial side reactions and solvent residues caused by the stepwise nano-sizing and surface modification in traditional technologies. It achieves efficient and low-consumption preparation of high-performance sulfide solid electrolytes under mild conditions.

[0007] Another aspect of the present invention relates to a sulfide solid electrolyte prepared by the aforementioned method.

[0008] The sulfide solid electrolyte features ultra-fine nanoparticles with a dense and stable lithium fluoride coating formed in situ on its surface. This unique structure endows the material with high specific surface area, low agglomeration characteristics, and extremely high interfacial chemical and electrochemical stability, thereby significantly improving ionic conductivity and effectively suppressing side reactions with the cathode material and water-oxygen corrosion.

[0009] Another aspect of the present invention relates to a solid-state battery, comprising a sulfide solid-state electrolyte prepared by the method for preparing the sulfide solid-state electrolyte or the sulfide solid-state electrolyte described above.

[0010] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention pioneers a novel, mild, and highly efficient "mechanical chemical in-situ fluorination" mechanism: It reveals and applies for the first time that chlorofluoromethanes such as chlorofluoromethane (R-11), dichlorofluoromethane (R-12), and chlorofluoromethane (R-13) can serve as highly efficient in-situ fluorinating agents. The core mechanism lies in utilizing the highly reactive sulfide surface created by acoustic resonance mechanical energy to preferentially attack the lower-energy C-Cl bonds in the reagent through nucleophilic substitution reactions, thereby triggering subsequent elimination or mechanically assisted cleavage reactions. Ultimately, this results in the in-situ formation of an ultra-stable coating layer centered on lithium fluoride (LiF) on the particle surface. This mechanism cleverly circumvents the thermodynamic barrier of directly breaking high-energy CF bonds, providing a completely new pathway for the surface modification of sulfide electrolytes.

[0011] This method achieves efficient one-step synergy between nano-sizing and interface passivation: It perfectly integrates efficient mechanical nano-sizing and advanced surface chemical modification processes into the same reactor and completes them simultaneously. It successfully solves the problems of process complexity, low efficiency and secondary pollution caused by step-by-step processing in traditional technologies, and realizes the synergistic control of the morphology and surface properties of sulfide electrolyte particles.

[0012] This endows the material with exceptional environmental and electrochemical stability: the generated LiF coating has an extremely wide electrochemical window (0-6V vs. Li / Li⁺) and excellent chemical inertness, fundamentally suppressing harmful side reactions between sulfide electrolytes and high-voltage cathode materials, significantly improving the cycle life and coulombic efficiency of all-solid-state batteries. Simultaneously, this dense coating greatly delays the erosion of the material by water and oxygen, significantly improving the material's air tolerance and processability.

[0013] This ensures the high performance and purity of the product: the resulting electrolyte powder not only has a small particle size and narrow distribution, but also possesses a high specific surface area and low agglomeration characteristics, which is highly beneficial for constructing a continuous and efficient ion transport network in the electrode. The entire process requires no grinding media, and reagent residues after the reaction are easily volatilized and removed, fundamentally eliminating foreign matter contamination and solvent residues, thus guaranteeing the purity and consistency of the product.

[0014] This approach offers excellent process flexibility and industrialization prospects: the aforementioned class of chlorofluoromethane reagents can be flexibly selected and optimized based on their boiling point and reactivity. This technical route boasts significant advantages such as simple equipment, short process, low energy consumption, no need for high-temperature post-treatment, and ease of scale-up, providing a highly promising new pathway for the preparation of high-performance, low-cost sulfide electrolytes and promoting their industrial application. Detailed Implementation

[0015] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. However, those skilled in the art will understand that the embodiments described below are some embodiments of the present invention, but not all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0016] One aspect of the present invention relates to a method for preparing a sulfide solid electrolyte, comprising the following steps: (a) The sulfide electrolyte and the inert solvent are mixed to obtain a slurry; (b) After adding grinding media and chlorofluoromethane to the slurry, acoustic resonance treatment and post-treatment are performed to obtain the sulfide solid electrolyte.

[0017] The method for preparing the sulfide solid electrolyte describes a novel integrated approach to "mechanical in-situ fluorination" by simultaneously performing two key steps—"acoustic resonance mechanical nano-sizing" and "in-situ fluorination with chlorofluoromethane"—in a low-temperature, inert reaction system. This method successfully solves the technical challenges of complex processes, low efficiency, interfacial side reactions, and solvent residues caused by the stepwise execution of nano-sizing and surface modification in traditional techniques. It achieves efficient and low-consumption preparation of high-performance sulfide solid electrolytes under mild conditions, demonstrating excellent process feasibility and industrialization prospects.

[0018] This invention provides a method for preparing fluorinated electrolytes based on low-temperature acoustic resonance-assisted mechanochemical in-situ fluorination. The method utilizes an inert alkane / ester solvent as the dispersion medium in a low-temperature liquid-cooled environment (e.g., -5°C), employing the high-intensity mechanical energy generated by an acoustic resonance mixer to efficiently nano-size the sulfide electrolyte, while simultaneously introducing a specific type of chlorofluoromethane reagent (general formula CCl4). x F 4-x (e.g., R-11, R-12, R-13), which allows it to undergo a unique in-situ fluorination reaction with the newly formed electrolyte surface under mechanical force, and finally obtains a sulfide electrolyte material with ultra-fine particle size, low agglomeration and ultra-stable lithium fluoride (LiF) coating on the surface after drying.

[0019] The core of this invention lies in abandoning the traditional approaches of "single mechanical crushing" or "stepwise coating," and instead employing a novel integrated approach of "mechanical-chemical in-situ fluorination" to simultaneously address the challenges of nano-sizing and interfacial stability in sulfide electrolytes. Its technological advancement is reflected in three aspects: First, a low-temperature, inert reaction environment was constructed to ensure process stability: By carefully selecting an inert alkane / ester mixed solvent that does not react with the sulfide electrolyte and maintaining a low temperature (e.g., -5°C) throughout the process, a liquid-phase dispersion system with "dual chemical and thermodynamic stability" was constructed. The low-temperature environment greatly suppressed any possible thermal side reactions and provided conditions for the liquid retention of the chlorofluoromethane reagent, thus ensuring the integrity of the main structure of the material from the source.

[0020] Secondly, it revolutionizes the energy transfer and surface modification methods: utilizing an acoustic resonance mixer to generate high-intensity, high-frequency mechanical vibration energy. This energy is efficiently transferred to the slurry through the dielectric zirconium beads. Its core function is no longer simple collision and grinding, but rather generating extremely strong shear forces, impact forces, and cavitation effects, which can efficiently "strip" electrolyte particles to the nanoscale. More importantly, this mechanical energy continuously creates fresh particle surfaces with high reactivity and drives in-situ chemical reactions between chlorofluoromethane reagents and these newly formed surfaces, achieving simultaneous nano-sizing and surface fluorination.

[0021] Third, it pioneers a mechanically driven in-situ fluorination mechanism, generating an ultra-stable interface: The most crucial feature of this invention lies in utilizing mechanical energy to trigger a unique surface chemical reaction. The highly reactive sulfide surface preferentially attacks the C-Cl bond in the chlorofluoromethane molecule via nucleophilic substitution, thereby initiating a subsequent elimination reaction, ultimately generating an inorganic coating layer with lithium fluoride (LiF) as its core in situ. This coating layer is firmly and densely bonded to the sulfide bulk and possesses an extremely wide electrochemical window, fundamentally altering the interfacial properties of the material.

[0022] The low-temperature inert solvent system solves the chemical and thermal decomposition problems during processing; the mechanical energy provided by acoustic resonance efficiently solves the two major problems of nano-fragmentation and initiating surface chemical reactions; and the chlorofluoromethane reagent, driven by mechanical force, solves the problem of in-situ construction of ultra-stable LiF interfaces through a unique reaction pathway. These interconnected technologies work synergistically to form a highly efficient, pure, low-consumption, and industrially scalable solution for preparing sulfide electrolytes.

[0023] Furthermore, the mass of the chlorofluoromethane is 1% to 10% of the mass of the sulfide electrolyte. This dosage range ensures the formation of a complete and dense LiF coating layer on the particle surface, while avoiding excessive reagents that could lead to excessive byproducts or erode the electrolyte's bulk structure, thus achieving an optimal balance between coating effect and material bulk properties.

[0024] Further, the fluorochloromethane includes at least one of: chloroform monofluorotrifluoromethane, dichloroform difluoromethane, or chloroform trifluoromethane. In some specific embodiments, the fluorochloromethane is any one of the above-mentioned fluorochloromethanes; or, the fluorochloromethane is a combination of any two of the above-mentioned fluorochloromethanes; or, the fluorochloromethane is a combination of any three of the above-mentioned fluorochloromethanes. When there are multiple fluorochloromethanes, they can be combined in any proportion. The selected reagent has moderate reactivity and a suitable boiling point, enabling it to preferentially undergo efficient in-situ fluorination reactions via the C-Cl bond breaking pathway under mechanical force, avoiding the high energy barrier of direct CF bond breaking, which is key to achieving the construction of a stable fluorination interface under mild conditions.

[0025] Furthermore, the acoustic resonance treatment temperature is -20~10℃. The low-temperature environment effectively suppresses possible thermal side reactions between chlorofluoromethane and solvents or electrolytes, ensuring the directional progress of the fluorination reaction and the thermal stability of the electrolyte bulk structure, which is a necessary condition for obtaining high-purity, high-performance products.

[0026] Furthermore, the acoustic resonance treatment time is 1-4 hours. This time range is sufficient to ensure that the particles are fully nano-sized and complete an effective surface fluorination reaction, while avoiding increased energy consumption and potential over-grinding risks caused by excessively long treatment times, thus achieving a balance between efficiency and effectiveness.

[0027] Furthermore, the vibration intensity of the acoustic resonance treatment is 50~100g. The high-intensity vibration provides sufficient mechanical energy, which can both efficiently break the particles to the nanoscale and activate their surface chemical reactivity, serving as the energy basis for simultaneously achieving the two processes of "nano-sizing" and "in-situ fluorination".

[0028] Furthermore, the inert solvent comprises alkanes and esters in a mass ratio of 3 to 5:1. This mixed solvent system combines the chemical inertness of alkanes with the wetting and dispersing properties of esters for sulfides, jointly constructing a stable and uniform liquid-phase reaction environment, which ensures process safety and promotes particle dispersion and reaction uniformity.

[0029] Furthermore, the alkanes include, but are not limited to, n-heptane and / or n-hexane. These straight-chain alkanes are chemically extremely stable, do not react with sulfide electrolytes or fluorinating agents, and have moderate boiling points that facilitate subsequent removal, making them ideal dispersion media for maintaining the purity of the reaction system.

[0030] Furthermore, the esters include, but are not limited to, butyl butyrate and / or ethyl acetate. The selected esters have a certain affinity for sulfide particles, which helps improve slurry flowability and prevent excessive particle aggregation. Simultaneously, their moderate polarity may facilitate mass transfer of the reactants, and they are easily volatilized and removed.

[0031] Furthermore, the diameter of the grinding media is 0.1~0.5mm. The small-sized grinding media provides a huge specific surface area and numerous contact points, which can generate dense and uniform micro-area impact and shear force in the acoustic resonance field. This is the key to achieving efficient and uniform nano-sizing and obtaining narrow-distribution ultrafine powders.

[0032] Furthermore, the grinding media includes, but is not limited to, at least one of: zirconia beads, alumina beads, or glass beads.

[0033] Furthermore, the mass ratio of the grinding media to the sulfide electrolyte is 10~30:1. This ratio ensures that there is a sufficient quantity of grinding media to effectively process all electrolyte particles, while avoiding problems such as energy loss, excessive temperature rise, and difficulties in subsequent separation caused by excessive media, thus optimizing process efficiency.

[0034] Furthermore, the solid content of the slurry is 20wt%~40wt%. This solid content range gives the slurry a suitable viscosity, which ensures effective energy transfer and collision frequency between the particles and the grinding media, while also ensuring good fluidity of the slurry and preventing a decrease in processing effect due to excessive thickness or thinness.

[0035] This invention does not specifically limit the type of sulfide electrolyte; conventional sulfide electrolytes in the art are applicable. In some specific embodiments, the sulfide electrolyte is a sulfide electrolyte containing lithium, phosphorus, sulfur, and halogens, preferably a sulfide electrolyte of the silver-germanium sulfide type, Li6PS5X (X = Cl, Br, I), or Li... 5.4 PS 4.4 Cl 1.6 Li 10 GeP2S12 Li7P3S 11 Or their elemental doped derivatives.

[0036] Furthermore, the sulfide electrolyte and the inert solvent are mixed together under an inert atmosphere.

[0037] Further, the post-processing includes: The slurry after the acoustic resonance treatment is filtered to separate and remove the grinding media; the resulting filtrate is dried under vacuum conditions at <80°C to completely remove volatile solvents and reaction residues, thus obtaining the sulfide solid electrolyte. The sulfide solid electrolyte has a LiF coating layer and is a low-agglomeration ultrafine electrolyte powder.

[0038] Another aspect of the present invention relates to a sulfide solid electrolyte prepared by the aforementioned method.

[0039] The sulfide solid electrolyte, prepared by the above method, achieves ultra-fine nanoparticle size and forms a dense and stable lithium fluoride coating layer in situ on its surface. This unique structure endows the material with high specific surface area, low agglomeration characteristics, and extremely high interfacial chemical and electrochemical stability, thereby significantly improving ionic conductivity and effectively suppressing side reactions with the cathode material and water-oxygen corrosion. This provides a core material foundation for constructing long-life, high-safety all-solid-state lithium batteries.

[0040] Furthermore, the particle size of the sulfide solid electrolyte is 50~150 nm.

[0041] Furthermore, the specific surface area (BET) of the sulfide solid electrolyte is greater than 30 m². 2 / g, and has a coating layer containing lithium fluoride (LiF) on its surface.

[0042] Furthermore, the sulfide solid electrolyte has a surface F element atomic percentage content greater than 5%, as measured by XPS.

[0043] Furthermore, the sulfide solid electrolyte is used to prepare the composite positive electrode layer, electrolyte separator layer, or as an additive to the negative electrode electrolyte of an all-solid-state lithium battery.

[0044] Another aspect of the present invention relates to a solid-state battery, comprising a sulfide solid-state electrolyte prepared by the method for preparing the sulfide solid-state electrolyte or the sulfide solid-state electrolyte described above.

[0045] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0046] Example 1 The method for preparing sulfide solid electrolyte provided in this embodiment includes the following steps: 1. Weigh 10g of sulfide solid electrolyte Li 5.4 PS 4.4 Cl 1.6 (LPSC) powder is placed in an argon-atmospheric glove box into a container containing 40g of strictly dehydrated and deoxygenated inert solvent, which includes n-heptane and butyl butyrate in a mass ratio of 4:1, and stirred to form a slurry. 2. Add 200g of zirconia beads with a diameter of 0.3mm to the slurry, and add 0.3g (3%) of chloroform (R-11). 3. Transfer the mixture to the tank of the acoustic resonance mixer and seal it; set the vibration intensity to 80g, start the liquid cooling system to maintain the temperature at -5°C, and process for 2 hours; 4. After the process is completed, the slurry is filtered to separate the zirconium beads. The resulting filtrate is dried at 80°C under vacuum for 12 hours to obtain the final ultrafine fluorinated sulfide solid electrolyte powder.

[0047] Example 2 The chlorofluoromethane reagent was replaced with 0.1 g (1%) of chlorofluoromethane (R-11), and all other conditions were exactly the same as in Example 1.

[0048] Example 3 The chlorofluoromethane reagent was replaced with 0.5 g (5%) of chlorofluoromethane (R-11), and all other conditions were exactly the same as in Example 1.

[0049] Example 4 The chlorofluoromethane reagent was replaced with an equal amount of dichlorofluoromethane (R-12) instead of chlorofluoromethane (R-11), and all other conditions were exactly the same as in Example 1.

[0050] Example 5 The acoustic resonance treatment time was shortened from 2 hours to 1 hour, while other conditions remained exactly the same as in Example 1.

[0051] Example 6 The acoustic resonance treatment time was extended from 2 hours to 3 hours, while other conditions remained exactly the same as in Example 1.

[0052] Example 7 Replace the sulfide electrolyte feedstock with an equal amount of Li 10 GeP2S 12 (LGPS), with all other conditions exactly the same as in Example 1.

[0053] Example 8 The mixed solvent was replaced by an equal amount of n-heptane / butyl butyrate with n-hexane / ethyl acetate (mass ratio 4:1), and all other conditions were exactly the same as in Example 1.

[0054] Comparative Example 1 (Traditional Dry Ball Milling) Weigh 10g of the same Li as in Example 1 5.4 PS 4.4 Cl 1.6 The powder was placed in a planetary ball mill jar along with 200g of 0.3mm diameter zirconia beads. The jar was sealed and placed in a planetary ball mill, where it was milled at 500 rpm for 2 hours. After milling, the contents of the jar were removed and passed through a 100-mesh sieve to separate the grinding beads from the powder, yielding electrolyte powder.

[0055] Comparative Example 2 (Traditional Wet Ball Milling) Weigh 10g of the same Li as in Example 1 5.4 PS 4.4 Cl 1.6 The powder, along with 200g of 0.3mm diameter zirconia beads and 40g of strictly dehydrated and deoxygenated n-heptane solvent, was placed in a planetary ball mill jar. The jar was sealed and placed in a planetary ball mill, where it was milled at 500 rpm for 2 hours. After milling, the slurry was removed from the jar, passed through a 100-mesh sieve, and the sieved slurry was dried at 80°C under vacuum for 12 hours to completely remove the solvent, yielding the electrolyte powder.

[0056] Comparative Example 3 (without fluorinating agent) Weigh 10g of the same Li as in Example 1 5.4 PS 4.4 Cl 1.6 The powder was placed in an argon-atmospheric glove box into a container containing 40g of a mixed solvent (n-heptane:butyl butyrate = 4:1) and stirred to form a slurry. 200g of 0.3mm diameter zirconia beads were added to the slurry. No chlorofluoromethane reagents were added. The mixture was transferred to an acoustic resonance mixer, set to a vibration intensity of 80g, and a temperature of -5°C for 2 hours. After treatment, the mixture was filtered and dried to obtain the electrolyte powder.

[0057] Comparative Example 4 (without cryogenic control) The operation procedure is exactly the same as in Example 1, but the liquid cooling system is turned off during the entire acoustic resonance treatment process, and the treatment is carried out at room temperature (about 25°C).

[0058] Particle size analysis Prepare an electrolyte suspension by mixing 20 mg of electrolyte powder and 5 mL of anhydrous anisole, then add 0.5 mL of dispersion and sonicate for 5 min. Pour the sonicated electrolyte dispersion into the sample cell of a laser particle size analyzer for particle size analysis and record the electrolyte D50 parameter.

[0059] Conductivity testing methods 1. Weigh 200mg of solid electrolyte, pour it into the mold, manually rotate it until it is even and flat, apply pressure of 108MPa, and hold the pressure for 1min; 2. Measure the thickness of the pressed electrolyte sheet using a micrometer and record the data; 3. Place the small mold into the metal kit, apply pressure of 216 MPa, and tighten the three knobs on the kit; 4. Use an electrochemical workstation to test the impedance of the model battery and record the electrolyte resistance.

[0060] F coating content test Weigh 20 mg of the treated sulfide electrolyte for XPS testing and read the surface S content data.

[0061] The relevant data is shown in Table 1.

[0062] Table 1 Comparison of precursor and electrolyte performance in the examples and comparative examples.

[0063] As shown in the table above, the electrolyte powders prepared in Examples 1-8 of this invention all exhibit ultrafine particle size (<110 nm) and high specific surface area (>30 m²). 2 The invention demonstrates high ionic conductivity and significantly increased surface F content (proving successful fluorination). In contrast, Comparative Example 1 (dry method) exhibited severe agglomeration; Comparative Example 2 (wet method) showed decreased conductivity due to solvent residue; Comparative Example 3 (no fluorinating agent) confirmed the crucial role of the fluorinating agent in inhibiting agglomeration and achieving nano-sizing; and Comparative Example 4 (no low temperature) showed that low temperature control is essential for maintaining the material's structure and properties. This invention successfully achieves the goal of one-step preparation of high-performance fluorinated coated sulfide electrolytes.

[0064] Although the present invention has been illustrated and described with specific embodiments, it should be understood that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; those skilled in the art should understand that modifications can be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein, without departing from the spirit and scope of the present invention; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention; therefore, this means that all such substitutions and modifications that fall within the scope of the present invention are included in the appended claims.

Claims

1. A method for producing a sulfide solid-state electrolyte, characterized by, The method comprises the following steps: (a) mixing a sulfide electrolyte and an inert solvent to obtain a slurry; (b) adding grinding media and fluoro-chloromethane to the slurry, and then performing acoustic resonance treatment and post-treatment to obtain the sulfide solid electrolyte.

2. The method for producing a sulfide solid-state electrolyte according to claim 1, characterized by, The mass of the fluoro-chloromethane is 1% to 10% of the mass of the sulfide electrolyte. And / or, the fluoro-chloromethane comprises at least one of monofluorotrichloromethane, difluorodichloromethane or trifluoromonochloromethane.

3. The method for producing a sulfide solid-state electrolyte according to claim 1, characterized by, The temperature of the acoustic resonance treatment is -20 to 10°C. And / or, the time of the acoustic resonance treatment is 1 to 4 hours.

4. The method of producing a sulfide solid-state electrolyte according to claim 1, characterized by, The vibration intensity of the acoustic resonance treatment is 50 to 100 g.

5. The method of producing a sulfide solid-state electrolyte according to claim 1, characterized by, The inert solvent comprises alkane and ester with a mass ratio of 3 to 5:

1. Preferably, the alkane comprises n-heptane and / or n-hexane. Preferably, the ester comprises butyl butyrate and / or ethyl acetate.

6. The method of producing a sulfide solid-state electrolyte according to claim 1, characterized by, The diameter of the grinding media is 0.1 to 0.5 mm.

7. The method of producing a sulfide solid-state electrolyte according to claim 1, characterized by, The mass ratio of the grinding media to the sulfide electrolyte is 10 to 30:

1.

8. The method of producing a sulfide solid-state electrolyte according to claim 1, characterized by, The solid content of the slurry is 20wt% to 40wt%.

9. The sulfide solid electrolyte prepared by the preparation method of the sulfide solid electrolyte according to any one of claims 1 to 8.

10. A solid state battery, characterized by, The sulfide solid electrolyte prepared by the preparation method of the sulfide solid electrolyte according to any one of claims 1 to 8 or the sulfide solid electrolyte according to claim 9.

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