Electrolyte material, electrode material for solid-state battery and preparation method thereof

Abstract

The application belongs to the technical field of battery materials, and particularly relates to an electrolyte material for a solid-state battery, an electrode material and a preparation method. POSS modified polyarylene ether ketone containing sulfonic acid groups, and cyclodextrin surface grafted scandium-containing zirconium oxide nano filler are respectively prepared, lithium tetrafluoroborate and lithium hexafluorophosphate are selected as compounded lithium salts, an electrolyte mixed solution is prepared by mixing the above components and a solvent, an electrolyte material is obtained by flow casting into a film, through the synergistic effect of multiple components, the oxygen index of the material is significantly improved, and good heat resistance is ensured, so that the material is better applied to the electrode material of the solid-state battery.

Description

Technical Field

[0001] This invention belongs to the field of battery materials technology, specifically relating to an electrolyte material, electrode material, and preparation method for solid-state batteries. Background Technology

[0002] High-energy-density and high-safety energy storage technologies have become the core driving force for the development of the new energy industry. While traditional lithium-ion batteries possess advantages such as high energy density and long cycle life, their ion transport system, based on organic liquid electrolytes, poses safety risks such as leakage and even combustion, severely hindering their development. To meet the high-performance power requirements of high-energy-density electric vehicles and new energy storage systems, developing highly safe and long-life rechargeable batteries has become a key task for the industry. Therefore, all-solid-state batteries using highly safe solid-state electrolytes to replace organic electrolytes have become a new development trend.

[0003] Compared to traditional flammable and leak-prone liquid electrolytes, solid-state electrolytes, with their excellent thermal stability, inherent flame retardancy, high mechanical strength, and superior electrochemical stability, are considered an ideal choice for improving battery energy density and ensuring battery safety. Solid-state electrolytes are mainly classified into three categories and five types: inorganic solid-state electrolytes (oxide electrolytes, sulfide electrolytes, and halide electrolytes), polymer solid-state electrolytes, and organic-inorganic composite solid-state electrolytes. Solid-state electrolytes, with their excellent mechanical stability, wide electrochemical window, and good thermal stability, have shown broad application potential and are expected to become the next-generation electrolyte development solution.

[0004] Chinese patent (publication number CN120199880A) discloses a solid electrolyte and its preparation method, a solid composite electrode, a solid battery, and a device. The solid electrolyte comprises an oxide electrolyte framework and a sulfide electrolyte. The oxide electrolyte framework has interconnected channels, and the sulfide electrolyte is attached to these channels. On one hand, the oxide electrolyte has high ionic conductivity, minimizing its impact on the loss of ionic conductivity of the sulfide electrolyte. On the other hand, the oxide electrolyte framework can minimize direct contact between the sulfide electrolyte and the positive and negative electrode materials within its internal channels, reducing the production of byproducts such as low-conductivity ions. This reduces the negative impact of unnecessary reactions of the sulfide electrolyte on battery performance, ensuring high ionic conductivity and interfacial stability in the solid battery, thus improving its application prospects. However, this patented technology lacks research on the flame-retardant and heat-resistant properties of the electrolyte material, resulting in poor applicability to extreme environments.

[0005] Therefore, how to prepare electrolyte materials for solid-state batteries through component design and the introduction of functional materials, effectively improve the heat resistance of the materials, and ensure good flame retardant properties so that they can be better applied to electrode materials, has become a research direction. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide an electrolyte material, electrode material, and preparation method for solid-state batteries. The present invention prepares POSS-modified polyarylether ketone containing sulfonic acid groups and zirconia nanofillers grafted with cyclodextrin, and then selects lithium tetrafluoroborate and lithium hexafluorophosphate as compound lithium salts. The above components are mixed with a solvent to obtain an electrolyte mixture, which is then cast into a film to obtain the electrolyte material. Through the synergistic effect of multiple components, the oxygen index of the material is significantly improved, and good heat resistance is ensured, making it better suited for use as an electrode material in solid-state batteries.

[0007] A first aspect of the present invention provides a method for preparing an electrolyte material for a solid-state battery, comprising the following steps: S1. Intermediate product A is prepared from 4,4'-difluorobenzophenone, 3,3'-diallylbisphenol S and 4,4-bis(4-hydroxyphenyl)valerate. Intermediate product A is sulfonated with sodium p-bromobenzenesulfonate to obtain intermediate product B. Then, amino POSS and intermediate product B are mixed and modified to obtain modified polyarylether ketone. S2. Zirconia composite powder is prepared using scandium oxide, zirconium oxychloride, and urea as raw materials. Then, the zirconium oxide composite powder is coupled with 3-aminopropyltriethoxysilane to obtain coupled zirconium oxide composite powder. Finally, the coupled zirconium oxide composite powder is mixed with β-cyclodextrin and grafted to obtain nanofiller. S3. The modified polyarylether ketone is added to N-methylpyrrolidone and stirred to mix. Then, lithium salt and the nanofiller are added and stirred to obtain an electrolyte mixture. S4. The electrolyte mixture is cast into a film to obtain an electrolyte material for solid-state batteries.

[0008] As a preferred technical solution of the present invention, the stirring conditions in step S3 are: temperature of 70~80℃ and time of 4~6h.

[0009] As a preferred technical solution of the present invention, the casting film step in step S4 is as follows: the electrolyte mixture is poured onto a polytetrafluoroethylene mold, and then vacuum dried at 80~90℃ for 10~12h, then vacuum dried at 110~120℃ for 6~8h, and finally vacuum dried at 140~150℃ for 1~2h.

[0010] As a preferred technical solution of the present invention, each component in step S3 includes, by weight: 80-100 parts of modified polyaryletherketone, 30-40 parts of lithium salt, 10-20 parts of nanofiller and 200-240 parts of N-methylpyrrolidone.

[0011] As a preferred technical solution of the present invention, the modified polyaryletherketone can be in the following weight proportions: 80 parts, 85 parts, 90 parts, 95 parts, or 100 parts, etc.

[0012] As a preferred embodiment of the present invention, the lithium salt may be expressed in parts by weight of 30, 32, 34, 36, 38, or 40, etc.

[0013] As a preferred embodiment of the present invention, the weight fraction of the nanofiller may be 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, or 20 parts, etc.

[0014] As a preferred technical solution of the present invention, the preparation steps of the intermediate product A are as follows: by weight, 20-24 parts of 4,4'-difluorobenzophenone, 18-22 parts of 3,3'-diallylbisphenol S, 10-12 parts of 4,4-bis(4-hydroxyphenyl)valeric acid and 14-16 parts of anhydrous potassium carbonate are mixed, then 80-100 parts of toluene and 140-160 parts of sulfolane are added and stirred for 2-4 hours. Under nitrogen protection, the temperature is raised to 116-120°C and refluxed for 3-5 hours, then the temperature is raised to 180-190°C and stirred for 8-10 hours. After washing with boiling water, the product is dried under vacuum to obtain intermediate product A.

[0015] As a preferred technical solution of the present invention, the preparation steps of the intermediate product B are as follows: by weight, 40-50 parts of p-bromobenzenesulfonyl chloride, 100-120 parts of deionized water and 100-120 parts of 1,4-dioxane are mixed, placed under a nitrogen atmosphere and heated to 100-110°C and stirred under reflux for 10-12 hours, and the mixture is rotary evaporated to obtain a yellow liquid. Then, 80-100 parts of 10 mg / mL sodium hydroxide ethanol solution are added to the yellow liquid and stirred for 2-4 hours to precipitate white crystals. The crystals are washed with anhydrous ethanol and dried to obtain sodium p-bromobenzenesulfonate. 20-24 parts of the intermediate product A, 14-16 parts of the sodium p-bromobenzenesulfonate, 1.4-1.8 parts of palladium triphenylphosphine acetate, and 2-4 parts of anhydrous potassium carbonate were added to 240-260 parts of N-methylpyrrolidone. The mixture was stirred at 38-40°C for 120-140 min under nitrogen protection, and then heated to 110-120°C and stirred for 12-16 h to obtain a mixture. The mixture was then transferred to 900-1000 parts of a 2 mol / L hydrochloric acid aqueous solution and soaked for 10-12 h. After washing with water, the mixture was dried under vacuum to obtain intermediate product B.

[0016] As a preferred embodiment of the present invention, the modification process is as follows: by weight, 8-12 parts of aminoPOSS are added to 400-500 parts of N-methylpyrrolidone and ultrasonically dispersed for 2-4 hours. Then, 20-24 parts of the intermediate product B, 2.4-2.6 parts of N,N'-dicyclohexylcarbodiimide and 0.1-0.3 parts of 4-dimethylaminopyridine are added and stirred. The mixture is then transferred to a reaction vessel and reacted at 150-160°C for 20-24 hours. The mixture is filtered to obtain a filtrate. Deionized water is added to the filtrate to obtain a precipitate. The precipitate is washed with anhydrous ethanol and dried under vacuum to obtain modified polyarylether ketone.

[0017] This invention uses 4,4'-difluorobenzophenone, 3,3'-diallylbisphenol S, and 4,4-bis(4-hydroxyphenyl)valeric acid as reactants, toluene and sulfolane as composite solvents, and anhydrous potassium carbonate as an acid-binding agent to synthesize intermediate product A containing carboxyl and allyl side groups. Then, under the action of palladium catalyst, the allyl side group of intermediate product A undergoes a coupling reaction with sodium p-bromobenzenesulfonate, introducing sulfonic acid groups onto the side chain. Finally, with the combined action of N,N'-dicyclohexylcarbodiimide and 4-dimethylaminopyridine, amino POSS is grafted onto the molecular chain to prepare POSS-modified polyarylether ketone containing sulfonic acid groups.

[0018] As a preferred embodiment of the present invention, the lithium salt is lithium tetrafluoroborate and lithium hexafluorophosphate; The mass ratio of lithium tetrafluoroborate to lithium hexafluorophosphate in the lithium salt is (1~2):1.

[0019] This invention selects lithium tetrafluoroborate and lithium hexafluorophosphate as lithium salts in the electrolyte material of solid-state batteries. It utilizes the chemical properties of the two lithium salts to make up for the shortcomings of a single lithium salt through synergistic effect, and effectively improves the overall performance of the material by controlling the mass ratio of the two.

[0020] As a preferred technical solution of the present invention, the preparation steps of the zirconia composite powder are as follows: by weight, 12-14 parts of scandium oxide are added to 200-240 parts of 3mol / L hydrochloric acid solution, the temperature is raised to 105-115℃ and stirred for 50-60 min, then 400-500 parts of 2mol / L zirconium oxychloride aqueous solution are added and mixed evenly, then 6-8 parts of urea and 0.6-0.8 parts of hexadecyltrimethylammonium bromide are added and stirred evenly, the mixture is transferred to a reaction vessel and reacted at 180-190℃ for 36-40 h, centrifuged, washed with water and dried to obtain zirconia composite powder.

[0021] As a preferred technical solution of the present invention, the coupling treatment step is as follows: by weight, 8-10 parts of the zirconium oxide composite powder are added to 400-500 parts of N-methylpyrrolidone and ultrasonically dispersed for 60-80 min, then 10-12 parts of 3-aminopropyltriethoxysilane are added, the mixture is heated to 90-100℃ and stirred for 6-8 h, centrifuged, washed with water, and dried to obtain the coupled zirconium oxide composite powder.

[0022] As a preferred embodiment of the present invention, the grafting treatment step is as follows: 12-14 parts of β-cyclodextrin are added to 400-500 parts of N-methylpyrrolidone and stirred to dissolve. Then, 10-12 parts of N,N'-carbonyldiimidazole are added and stirred for 100-120 min. Then, 8-10 parts of the coupled zirconia composite powder are added and stirred for grafting for 26-30 h. The mixture is washed with water and dried to obtain the nanofiller.

[0023] This invention first synthesizes scandium-containing zirconium oxide composite powder via a hydrothermal method using scandium oxide as the scandium source, zirconium oxychloride as the zirconium source, urea as the precipitant, and hexadecyltrimethylammonium bromide as the surfactant. Then, a silane coupling agent is used for surface modification to introduce amino groups onto the powder surface. Finally, N,N'-carbonyldiimidazole is used to activate β-cyclodextrin and graft it onto the amino-containing powder to obtain scandium-containing zirconium oxide nanofiller grafted onto the cyclodextrin surface.

[0024] A second aspect of the present invention provides an electrolyte material for solid-state batteries prepared by the preparation method described in the first aspect.

[0025] A third aspect of the present invention provides an electrode material for a solid-state battery, comprising a wafer and an electrolyte material prepared by the preparation method described in the first aspect.

[0026] Compared with the prior art, the present invention has the following beneficial effects: (1) The modified polyaryletherketone POSS of the present invention will jump to the surface to form a dense silicon-containing barrier layer under high temperature conditions, which isolates oxygen from the contact between the internal polymer. At the same time, the aromatic structure of the molecular chain itself has a high carbonization rate, and the sulfonic acid group can synergistically form a high-strength carbon layer, which comprehensively improves the oxygen index of the material. POSS has an inorganic siloxane structure, which can act as a molecular anchor to restrict the thermal movement of the polymer main chain segments. Combined with the heat-resistant aromatic ring on the polyaryletherketone main chain, it significantly improves the heat resistance.

[0027] (2) The lithium tetrafluoroborate in the compound lithium salt of the present invention has high thermal stability and can also form a stable complex with the decomposition products of lithium hexafluorophosphate, which delays the high-temperature decomposition process of the electrolyte as a whole and improves the heat resistance of the material. Under high temperature conditions, the boron element of lithium tetrafluoroborate participates in the polymer cross-linking reaction to form a boron-containing glassy coating layer, which effectively blocks the heat transfer inward and the diffusion of combustible pyrolysis gas outward. The phosphorus element of lithium hexafluorophosphate volatilizes into the gas phase during the combustion process and captures the free radicals in the polymer combustion chain reaction. The condensed phase flame retardancy of lithium tetrafluoroborate and the gas phase flame retardancy of lithium hexafluorophosphate work synergistically to achieve good flame retardant performance of the material.

[0028] (3) The oxygen vacancies of the scandium-containing zirconium oxide in the nanofiller of the present invention can capture the free radicals generated in the early stage of polymer pyrolysis and inhibit the autocatalytic degradation chain reaction. β-cyclodextrin can provide an anchoring effect that greatly restricts the thermal movement of polymer chain segments, thereby improving the heat resistance of the material. Zirconia itself is an excellent refractory material. The solid solution lattice formed after doping with scandium is more stable and forms a non-combustible rigid skeleton in the material. β-cyclodextrin undergoes dehydration and carbonization at high temperature to form a dense aromatic carbon layer, which together improves the oxygen index.

[0029] (4) The modified polyaryletherketone of this invention contains POSS, which works in conjunction with the scandium-containing zirconium oxide nanofiller to construct an "inorganic-carbon" composite reinforced protective layer in the condensed phase, greatly hindering the diffusion of external oxygen into the interior and the escape of internal combustible volatiles. The boron-containing species complexed in the cyclodextrin cavity and the decomposition products of POSS can synergistically capture free radicals, inhibiting flame propagation and achieving gas-phase flame retardancy. Through the dual defense mechanism of "gas-phase dilution + condensed phase barrier", the oxygen index of the material is greatly improved. The β-cyclodextrin on the surface of the nanofiller interacts with the sulfonic acid groups in the modified polyaryletherketone matrix through hydroxyl groups to form a network structure. Combined with POSS and scandium-containing zirconium oxide, which have good high-temperature resistance, the heat resistance of the material is significantly increased. Attached Figure Description

[0030] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below.

[0031] Figure 1 The image shows the XRD pattern of the nanofiller in Example 1.

[0032] Figure 2 This is an XPS image of the nanofiller in Example 1. Detailed Implementation

[0033] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0034] The sources of some components in the examples and comparative examples are as follows: 4,4'-Difluorobenzophenone, CAS No. 345-92-6, purchased from Shanghai Maclean Biochemical Technology Co., Ltd. 3,3'-Diallylbisphenol S, CAS No. 41481-66-7, was purchased from Wuhan Beiguofeng Chemical Co., Ltd. 4,4-Bis(4-hydroxyphenyl)valerate, CAS No. 126-00-1, purchased from Shanghai Maclean Biochemical Technology Co., Ltd. Anhydrous potassium carbonate, CAS No. 584-08-7, purchased from Sinopharm Chemical Reagent Co., Ltd. p-Bromobenzenesulfonyl chloride, CAS No. 98-58-8, was purchased from Sinopharm Chemical Reagent Co., Ltd. 1,4-Dioxane, CAS No. 123-91-1, purchased from Sinopharm Chemical Reagent Co., Ltd. Triphenylphosphine palladium acetate, CAS No. 14588-08-0, was purchased from Shanghai Maclean Biochemical Technology Co., Ltd. Amino POSS, product number Q0247615, was purchased from Xi'an Qiyue Biotechnology Co., Ltd. N,N'-Dicyclohexylcarbodiimide, CAS No. 538-75-0, was purchased from Shanghai Maclean Biochemical Technology Co., Ltd. 4-Dimethylaminopyridine, CAS No. 1122-58-3, was purchased from Shanghai Maclean Biochemical Technology Co., Ltd. Lithium tetrafluoroborate, CAS No. 14283-07-9, was purchased from Shanghai Maclean Biochemical Technology Co., Ltd. Lithium hexafluorophosphate, CAS No. 21324-40-3, was purchased from Shanghai Maclean Biochemical Technology Co., Ltd. Scandium oxide, CAS No. 12060-08-1, was purchased from Sinopharm Chemical Reagent Co., Ltd. Zirconium oxychloride, CAS No. 7699-43-6, was purchased from Sinopharm Chemical Reagent Co., Ltd. Urea, CAS No. 57-13-6, purchased from Shanghai Maclean Biochemical Technology Co., Ltd. Hexadecyltrimethylammonium bromide, CAS No. 57-09-0, was purchased from Shanghai Maclean Biochemical Technology Co., Ltd. 3-Aminopropyltriethoxysilane, CAS No. 919-30-2, was purchased from Shanghai Maclean Biochemical Technology Co., Ltd. β-Cyclodextrin, CAS No. 7585-39-9, was purchased from Sinopharm Chemical Reagent Co., Ltd. N,N'-carbonyldiimidazole, CAS No. 530-62-1, was purchased from Shanghai Maclean Biochemical Technology Co., Ltd. Example

[0035] This embodiment provides a method for preparing an electrolyte material for solid-state batteries, including the following steps: S1. By weight, 24 parts of 4,4'-difluorobenzophenone, 22 parts of 3,3'-diallylbisphenol S, 12 parts of 4,4-bis(4-hydroxyphenyl)valeric acid, and 16 parts of anhydrous potassium carbonate were mixed, then 100 parts of toluene and 160 parts of sulfolane were added and stirred for 4 hours. Under nitrogen protection, the mixture was heated to 120°C and refluxed for 3 hours, then heated to 190°C and stirred for 8 hours. The mixture was washed with boiling water and dried under vacuum to obtain intermediate product A. 50 parts of p-bromobenzenesulfonyl chloride, 120 parts of deionized water, and 120 parts of 1,4-dioxane were mixed and placed under nitrogen protection at 110°C and stirred under reflux for 10 hours. The mixture was rotary evaporated to obtain a yellow liquid. Then, 100 parts of 10 mg / mL sodium hydroxide ethanol solution were added to the yellow liquid and stirred for 4 hours to precipitate white crystals. The crystals were washed with anhydrous ethanol and dried to obtain sodium p-bromobenzenesulfonate. 24 parts of the intermediate product A were added to the mixture. 16 parts of the sodium p-bromobenzenesulfonate, 1.8 parts of palladium triphenylphosphine acetate, and 4 parts of anhydrous potassium carbonate were added to 260 parts of N-methylpyrrolidone. The mixture was stirred at 40°C for 120 min under nitrogen protection, then heated to 120°C and stirred for 12 h to obtain a mixture. The mixture was then transferred to 1000 parts of 2 mol / L hydrochloric acid aqueous solution and soaked for 12 h. After washing with water, the mixture was vacuum dried to obtain intermediate product B. 12 parts of aminoPOSS were added to 500 parts of N-methylpyrrolidone and ultrasonically dispersed for 4 h. Then, 24 parts of intermediate product B, 2.6 parts of N,N'-dicyclohexylcarbodiimide, and 0.3 parts of 4-dimethylaminopyridine were added and stirred. The mixture was transferred to a reactor and reacted at 160°C for 20 h. The mixture was filtered to obtain a filtrate. Deionized water was added to the filtrate to obtain a precipitate. The precipitate was washed with anhydrous ethanol and vacuum dried to obtain modified polyarylether ketone.

[0036] S2. By weight, 14 parts of scandium oxide were added to 240 parts of 3 mol / L hydrochloric acid solution, heated to 115℃ and stirred for 50 min. Then, 500 parts of 2 mol / L zirconium oxychloride aqueous solution were added and mixed evenly. Next, 8 parts of urea and 0.8 parts of hexadecyltrimethylammonium bromide were added and stirred evenly. The mixture was transferred to a reaction vessel and reacted at 190℃ for 36 h. After centrifugation, washing with water, and drying, zirconium oxide composite powder was obtained. 10 parts of the zirconium oxide composite powder were added to 500 parts of N The mixture was ultrasonically dispersed in N-methylpyrrolidone for 80 min, then 12 parts of 3-aminopropyltriethoxysilane were added, the mixture was heated to 100℃ and stirred for 6 h, centrifuged, washed with water, and dried to obtain coupled zirconia composite powder. 14 parts of β-cyclodextrin were added to 500 parts of N-methylpyrrolidone and stirred to dissolve, then 112 parts of N,N'-carbonyldiimidazole were added and stirred for 120 min, then 10 parts of the coupled zirconia composite powder were added and stirred for grafting for 30 h, washed with water, and dried to obtain nanofiller.

[0037] S3. Add 100 parts of the modified polyarylether ketone to 240 parts of N-methylpyrrolidone and stir to mix. Then add 40 parts of lithium salt (20 parts of lithium tetrafluoroborate and 20 parts of lithium hexafluorophosphate) and 20 parts of the nanofiller and stir (temperature 80°C, time 4h) to obtain electrolyte mixture. S4. Pour the electrolyte mixture onto a polytetrafluoroethylene mold, then vacuum dry it at 90°C for 10 hours, then vacuum dry it at 120°C for 6 hours, and finally vacuum dry it at 150°C for 1 hour to obtain the electrolyte material for solid-state batteries. Example

[0038] This embodiment provides a method for preparing an electrolyte material for solid-state batteries, including the following steps: S1. By weight, 20 parts of 4,4'-difluorobenzophenone, 18 parts of 3,3'-diallylbisphenol S, 10 parts of 4,4-bis(4-hydroxyphenyl)valeric acid, and 14 parts of anhydrous potassium carbonate were mixed, and then 80 parts of toluene and 140 parts of sulfolane were added and stirred for 2 hours. Under nitrogen protection, the mixture was heated to 116°C and refluxed for 5 hours, then heated to 180°C and stirred for 10 hours. The mixture was washed with boiling water and dried under vacuum to obtain intermediate product A. 40 parts of p-bromobenzenesulfonyl chloride, 100 parts of deionized water, and 100 parts of 1,4-dioxane were mixed and placed under nitrogen protection at 100°C and stirred under reflux for 10 hours. The mixture was rotary evaporated to obtain a yellow liquid. Then, 80 parts of 10 mg / mL sodium hydroxide ethanol solution were added to the yellow liquid and stirred for 2 hours to precipitate white crystals. The crystals were washed with anhydrous ethanol and dried to obtain sodium p-bromobenzenesulfonate. 20 parts of the intermediate product were added to the mixture. A. 14 parts of the aforementioned sodium p-bromobenzenesulfonate, 1.4 parts of palladium triphenylphosphine acetate, and 2 parts of anhydrous potassium carbonate were added to 240 parts of N-methylpyrrolidone. The mixture was stirred at 38°C for 120 min under nitrogen protection, then heated to 110°C and stirred for 16 h to obtain a mixture. The mixture was then transferred to 900 parts of 2 mol / L hydrochloric acid aqueous solution and soaked for 10 h. After washing with water and vacuum drying, intermediate product B was obtained. 8 parts of aminoPOSS were added to 400 parts of N-methylpyrrolidone and ultrasonically dispersed for 2 h. Then, 20 parts of intermediate product B, 2.4 parts of N,N'-dicyclohexylcarbodiimide, and 0.1 parts of 4-dimethylaminopyridine were added and stirred. The mixture was transferred to a reaction vessel and reacted at 150°C for 24 h. The filtrate was filtered, and deionized water was added to the filtrate to obtain a precipitate. The precipitate was washed with anhydrous ethanol and vacuum dried to obtain modified polyarylether ketone.

[0039] S2. By weight, 12 parts of scandium oxide were added to 200 parts of 3 mol / L hydrochloric acid solution, heated to 105℃ and stirred for 60 min. Then, 400 parts of 2 mol / L zirconium oxychloride aqueous solution were added and mixed evenly. Next, 6 parts of urea and 0.6 parts of hexadecyltrimethylammonium bromide were added and stirred evenly. The mixture was then transferred to a reaction vessel and reacted at 180℃ for 40 h. After centrifugation, washing with water, and drying, zirconium oxide composite powder was obtained. 8 parts of the zirconium oxide composite powder were added to 400 parts of... The mixture was ultrasonically dispersed in N-methylpyrrolidone for 60 min, then 10 parts of 3-aminopropyltriethoxysilane were added, the mixture was heated to 90℃ and stirred for 8 h, centrifuged, washed with water, and dried to obtain coupled zirconia composite powder. 12 parts of β-cyclodextrin were added to 400 parts of N-methylpyrrolidone and stirred to dissolve, then 10 parts of N,N'-carbonyldiimidazole were added and stirred for 100 min, then 8 parts of the coupled zirconia composite powder were added and stirred for grafting for 26 h, washed with water, and dried to obtain nanofiller.

[0040] S3. Add 80 parts of the modified polyarylether ketone to 200 parts of N-methylpyrrolidone and stir to mix. Then add 30 parts of lithium salt (20 parts of lithium tetrafluoroborate and 10 parts of lithium hexafluorophosphate) and 10 parts of the nanofiller and stir (temperature 70°C, time 6h) to obtain an electrolyte mixture. S4. Pour the electrolyte mixture onto a polytetrafluoroethylene mold, then vacuum dry it at 80°C for 12 hours, then vacuum dry it at 110°C for 8 hours, and finally vacuum dry it at 140°C for 2 hours to obtain the electrolyte material for solid-state batteries. Example

[0041] This embodiment provides a method for preparing an electrolyte material for solid-state batteries, including the following steps: S1. By weight, 22 parts of 4,4'-difluorobenzophenone, 20 parts of 3,3'-diallylbisphenol S, 11 parts of 4,4-bis(4-hydroxyphenyl)valeric acid, and 15 parts of anhydrous potassium carbonate were mixed, and then 90 parts of toluene and 150 parts of sulfolane were added and stirred for 3 hours. Under nitrogen protection, the mixture was heated to 118°C and refluxed for 4 hours, then heated to 185°C and stirred for 9 hours. The mixture was washed with boiling water and dried under vacuum to obtain intermediate product A. 45 parts of p-bromobenzenesulfonyl chloride, 110 parts of deionized water, and 110 parts of 1,4-dioxane were mixed and placed under nitrogen protection at 105°C and stirred under reflux for 11 hours. The mixture was rotary evaporated to obtain a yellow liquid. Then, 90 parts of 10 mg / mL sodium hydroxide ethanol solution were added to the yellow liquid and stirred for 3 hours to precipitate white crystals. The crystals were washed with anhydrous ethanol and dried to obtain sodium p-bromobenzenesulfonate. 22 parts of the intermediate product A were added to the mixture. 15 parts of the sodium p-bromobenzenesulfonate, 1.6 parts of palladium triphenylphosphine acetate, and 3 parts of anhydrous potassium carbonate were added to 250 parts of N-methylpyrrolidone. The mixture was stirred at 39°C for 130 min under nitrogen protection, then heated to 115°C and stirred for 14 h to obtain a mixture. The mixture was then transferred to 950 parts of 2 mol / L hydrochloric acid aqueous solution and soaked for 11 h. After washing with water, the mixture was vacuum dried to obtain intermediate product B. 10 parts of aminoPOSS were added to 450 parts of N-methylpyrrolidone and ultrasonically dispersed for 3 h. Then, 22 parts of intermediate product B, 2.5 parts of N,N'-dicyclohexylcarbodiimide, and 0.2 parts of 4-dimethylaminopyridine were added and stirred. The mixture was transferred to a reactor and reacted at 155°C for 22 h. The mixture was filtered to obtain a filtrate. Deionized water was added to the filtrate to obtain a precipitate. The precipitate was washed with anhydrous ethanol and vacuum dried to obtain modified polyarylether ketone.

[0042] S2. By weight, 13 parts of scandium oxide were added to 220 parts of 3 mol / L hydrochloric acid solution, heated to 110℃ and stirred for 55 min. Then, 450 parts of 2 mol / L zirconium oxychloride aqueous solution were added and mixed evenly. Next, 7 parts of urea and 0.7 parts of hexadecyltrimethylammonium bromide were added and stirred evenly. The mixture was transferred to a reaction vessel and reacted at 185℃ for 38 h. After centrifugation, washing with water, and drying, zirconium oxide composite powder was obtained. 9 parts of the zirconium oxide composite powder were added to 450 parts of... The mixture was ultrasonically dispersed in N-methylpyrrolidone for 70 min, then 11 parts of 3-aminopropyltriethoxysilane were added, the mixture was heated to 95℃ and stirred for 7 h, centrifuged, washed with water, and dried to obtain coupled zirconia composite powder. 13 parts of β-cyclodextrin were added to 450 parts of N-methylpyrrolidone and stirred to dissolve, then 11 parts of N,N'-carbonyldiimidazole were added and stirred for 110 min, then 9 parts of the coupled zirconia composite powder were added and stirred for grafting for 28 h, washed with water, and dried to obtain nanofiller.

[0043] S3. Add 90 parts of the modified polyarylether ketone to 220 parts of N-methylpyrrolidone and stir to mix. Then add 35 parts of lithium salt (20 parts of lithium tetrafluoroborate and 15 parts of lithium hexafluorophosphate) and 15 parts of the nanofiller and stir (temperature 75°C, time 5h) to obtain an electrolyte mixture. S4. Pour the electrolyte mixture onto a polytetrafluoroethylene mold, then vacuum dry it at 85°C for 11 hours, then vacuum dry it at 115°C for 7 hours, and finally vacuum dry it at 145°C for 1.5 hours to obtain the electrolyte material for solid-state batteries.

[0044] Comparative Example 1 The difference between this comparative example and Example 1 is that commercially available common polyaryletherketone is used instead of modified polyaryletherketone.

[0045] Comparative Example 2 The difference between this comparative example and Example 1 is that 40 parts of lithium salt were replaced with 30 parts of lithium tetrafluoroborate and 10 parts of lithium hexafluorophosphate.

[0046] Comparative Example 3 The difference between this comparative example and Example 1 is that 40 parts of lithium salt were replaced with 10 parts of lithium tetrafluoroborate and 30 parts of lithium hexafluorophosphate.

[0047] Comparative Example 4 The difference between this comparative example and Example 1 is that zirconium oxide powder is used instead of nanofiller.

[0048] The performance of the electrolyte materials provided in the above embodiments and comparative examples was tested using the following methods: (1) Oxygen index test: The test shall be conducted in accordance with the requirements of GB / T 2406.2-2009 Determination of combustion behavior of plastics by oxygen index method - Part 2: Room temperature test.

[0049] (2) Heat resistance test: The test shall be conducted in accordance with the requirements of GB / T 27761-2011 Test method for weight loss and residual amount of thermogravimetric analyzer. The residual mass at 600℃ shall be used to evaluate the heat resistance.

[0050] (3) Tensile property test: The test shall be conducted in accordance with the requirements of GB / T 1040.1-2025 Determination of tensile properties of plastics Part 1: General Rules.

[0051] The performance test data above are shown in Table 1.

[0052] Table 1 Performance Test Results Oxygen index (%) Residual mass at 600℃ (%) Tensile strength (MPa) Example 1 44.8 39.6 118.3 Example 2 44.1 38.9 116.5 Example 3 44.5 39.2 117.6 Comparative Example 1 35.2 30.6 109.8 Comparative Example 2 40.4 35.8 114.2 Comparative Example 3 39.7 35.3 113.6 Comparative Example 4 36.9 32.1 101.7 As can be seen from the above, the present invention prepares POSS-modified polyarylether ketone containing sulfonic acid groups and zirconia nanofillers grafted with cyclodextrin, and then selects lithium tetrafluoroborate and lithium hexafluorophosphate as compound lithium salts. The above components and solvents are mixed to prepare an electrolyte mixture, which is then cast into a film to obtain an electrolyte material (Examples 1 to 3), which has the best comprehensive performance.

[0053] Compared to Example 1, using commercially available common polyaryletherketone (PGEK) instead of modified PGEK resulted in a decrease in the oxygen index and a deterioration in heat resistance due to the lack of the modified PGEK effect (Comparative Example 1). Compared to Example 1, 40 parts of lithium salt were replaced with 30 parts of lithium tetrafluoroborate and 10 parts of lithium hexafluorophosphate. Due to the excessive amount of lithium tetrafluoroborate, the compounding effect was poor, resulting in a decrease in the oxygen index and a deterioration in heat resistance (Comparative Example 2). Compared to Example 1, 40 parts of lithium salt were replaced with 10 parts of lithium tetrafluoroborate and 30 parts of lithium hexafluorophosphate. Due to the excessive amount of lithium hexafluorophosphate, the compounding effect was poor, resulting in a decrease in the oxygen index and a deterioration in heat resistance (Comparative Example 3). Compared to Example 1, using zirconium oxide powder instead of nanofiller resulted in a decrease in the oxygen index and a deterioration in heat resistance due to the lack of the nanofiller effect (Comparative Example 4).

Claims

1. A method for preparing an electrolyte material for solid-state batteries, characterized in that, Includes the following steps: S1. Intermediate product A is prepared from 4,4'-difluorobenzophenone, 3,3'-diallylbisphenol S and 4,4-bis(4-hydroxyphenyl)valerate. Intermediate product A is sulfonated with sodium p-bromobenzenesulfonate to obtain intermediate product B. Then, amino POSS and intermediate product B are mixed and modified to obtain modified polyarylether ketone. S2. Zirconia composite powder is prepared using scandium oxide, zirconium oxychloride, and urea as raw materials. Then, the zirconium oxide composite powder is coupled with 3-aminopropyltriethoxysilane to obtain coupled zirconium oxide composite powder. Finally, the coupled zirconium oxide composite powder is mixed with β-cyclodextrin and grafted to obtain nanofiller. S3. The modified polyarylether ketone is added to N-methylpyrrolidone and stirred to mix. Then, lithium salt and the nanofiller are added and stirred to obtain an electrolyte mixture. S4. The electrolyte mixture is cast into a film to obtain an electrolyte material for solid-state batteries.

2. The method for preparing an electrolyte material for a solid-state battery according to claim 1, characterized in that, The components in step S3, by weight, include: 80-100 parts of modified polyarylether ketone, 30-40 parts of lithium salt, 10-20 parts of nanofiller, and 200-240 parts of N-methylpyrrolidone.

3. The method for preparing an electrolyte material for a solid-state battery according to claim 1, characterized in that, The preparation steps of intermediate product A are as follows: by weight, 20-24 parts of 4,4'-difluorobenzophenone, 18-22 parts of 3,3'-diallylbisphenol S, 10-12 parts of 4,4-bis(4-hydroxyphenyl)valeric acid and 14-16 parts of anhydrous potassium carbonate are mixed, then 80-100 parts of toluene and 140-160 parts of sulfolane are added and stirred for 2-4 hours. Under nitrogen protection, the temperature is raised to 116-120°C and refluxed for 3-5 hours, then the temperature is raised to 180-190°C and stirred for 8-10 hours. After washing with boiling water, the mixture is dried under vacuum to obtain intermediate product A.

4. The method for preparing an electrolyte material for a solid-state battery according to claim 1, characterized in that, The preparation steps of the intermediate product B are as follows: by weight, 40-50 parts of p-bromobenzenesulfonyl chloride, 100-120 parts of deionized water and 100-120 parts of 1,4-dioxane are mixed, placed under a nitrogen atmosphere and heated to 100-110℃ and stirred under reflux for 10-12 hours. A yellow liquid is obtained by rotary evaporation. Then, 80-100 parts of 10 mg / mL sodium hydroxide ethanol solution are added to the yellow liquid and stirred for 2-4 hours to precipitate white crystals. The crystals are washed with anhydrous ethanol and dried to obtain sodium p-bromobenzenesulfonate. 20-24 parts of the intermediate product A, 14-16 parts of the sodium p-bromobenzenesulfonate, 1.4-1.8 parts of palladium triphenylphosphine acetate, and 2-4 parts of anhydrous potassium carbonate were added to 240-260 parts of N-methylpyrrolidone. The mixture was stirred at 38-40°C for 120-140 min under nitrogen protection, and then heated to 110-120°C and stirred for 12-16 h to obtain a mixture. The mixture was then transferred to 900-1000 parts of a 2 mol / L hydrochloric acid aqueous solution and soaked for 10-12 h. After washing with water, the mixture was dried under vacuum to obtain intermediate product B.

5. The method for preparing an electrolyte material for a solid-state battery according to claim 1, characterized in that, The modification process is as follows: by weight, 8-12 parts of aminoPOSS are added to 400-500 parts of N-methylpyrrolidone and ultrasonically dispersed for 2-4 hours. Then, 20-24 parts of the intermediate product B, 2.4-2.6 parts of N,N'-dicyclohexylcarbodiimide and 0.1-0.3 parts of 4-dimethylaminopyridine are added and stirred. The mixture is then transferred to a reaction vessel and reacted at 150-160°C for 20-24 hours. The mixture is filtered to obtain a filtrate. Deionized water is added to the filtrate to obtain a precipitate. The precipitate is washed with anhydrous ethanol and dried under vacuum to obtain modified polyarylether ketone.

6. The method for preparing an electrolyte material for a solid-state battery according to claim 1, characterized in that, The lithium salt is lithium tetrafluoroborate and lithium hexafluorophosphate; The mass ratio of lithium tetrafluoroborate to lithium hexafluorophosphate in the lithium salt is (1~2):

1.

7. The method for preparing an electrolyte material for a solid-state battery according to claim 1, characterized in that, The preparation steps of the zirconia composite powder are as follows: by weight, 12-14 parts of scandium oxide are added to 200-240 parts of 3mol / L hydrochloric acid solution, the temperature is raised to 105-115℃ and stirred for 50-60 min, then 400-500 parts of 2mol / L zirconium oxychloride aqueous solution are added and mixed evenly, then 6-8 parts of urea and 0.6-0.8 parts of hexadecyltrimethylammonium bromide are added and stirred evenly, the mixture is transferred to a reaction vessel and reacted at 180-190℃ for 36-40 h, centrifuged, washed with water and dried to obtain zirconia composite powder.

8. The method for preparing an electrolyte material for a solid-state battery according to claim 1, characterized in that, The coupling treatment steps are as follows: by weight, 8-10 parts of the zirconia composite powder are added to 400-500 parts of N-methylpyrrolidone and ultrasonically dispersed for 60-80 min, then 10-12 parts of 3-aminopropyltriethoxysilane are added, the temperature is raised to 90-100℃ and stirred for 6-8 h, centrifuged, washed with water and dried to obtain the coupled zirconia composite powder; The grafting process is as follows: 12-14 parts of β-cyclodextrin are added to 400-500 parts of N-methylpyrrolidone and stirred to dissolve. Then, 10-12 parts of N,N'-carbonyldiimidazole are added and stirred for 100-120 min. Next, 8-10 parts of the coupled zirconia composite powder are added and stirred for grafting for 26-30 h. The mixture is then washed with water and dried to obtain the nanofiller.

9. An electrolyte material for solid-state batteries, characterized in that, It is prepared by the preparation method according to any one of claims 1 to 8.

10. An electrode material for a solid-state battery, characterized in that, Includes the electrolyte material prepared by the preparation method according to any one of claims 1 to 8.

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