Electrolyte based on acidic ionic liquid and preparation method thereof

Abstract

The invention discloses an electrolyte based on acidic ionic liquid and a preparation method of the electrolyte, particularly relates to the technical field of electrolytes, and relates to the electrolyte based on the acidic ionic liquid and the preparation method of the electrolyte. The electrolyte based on the acidic ionic liquid is prepared from 1-vinyl-3-(3-sulfopropyl) imidazole, concentrated sulfuric acid, dibenzoyl peroxide, titanium dioxide and zirconium oxide; by introducing metal oxide subjected to differentiated surface treatment, a biphase continuous interpenetrating network is constructed in a polymer matrix by virtue of electrostatic interaction and interface design, a rapid interface ion transmission channel and a firm mechanical supporting framework are synchronously provided, and the chemical corrosion resistance and physical deformation resistance of the material are remarkably enhanced; the electrolyte stability is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrolyte, more particularly, the present application relates to an electrolyte based on acidic ionic liquid and a preparation method thereof. BACKGROUND

[0002] Lead-acid battery as an important electrochemical energy storage device, is widely used in the field of transportation, communication backup power supply, etc., however, the traditional lead-acid battery uses liquid sulfuric acid electrolyte, which has the functions of ion transmission and charge path construction, participating in electrode redox reaction, system stability and performance control; therefore, it is of great significance to propose a new electrolyte system to enhance its safety and environmental friendliness.

[0003] The preparation ingredients of the traditional electrolyte include sulfuric acid, water and additives; among them, sulfuric acid as a conductive medium, ionizes in water, provides ion conduction path, is the basis of charge transfer inside the battery, and in the charging and discharging process, sulfuric acid has reversible reaction with lead and lead oxide at the positive and negative electrodes, and the concentration change directly affects the battery voltage and capacity, and affects the electrolyte density; water as a solvent dissolves sulfuric acid to form an ion conductive liquid phase environment, which affects the viscosity, freezing point, boiling point and conductivity of the electrolyte, and also affects the dissolution and recrystallization process of lead sulfate; additives generally include sulfate and silicon dioxide, which are used to inhibit dendrite growth, improve electrode interface stability or prolong battery life.

[0004] However, when it is actually used, there are still some shortcomings, such as poor safety, the traditional electrolyte uses high concentration sulfuric acid which has strong corrosive to metal, plastic and human tissue, liquid electrolyte is easy to leak when the battery is collided, tilted or sealed aging, which causes short circuit, fire and even explosion hazards; serious pollution, sulfuric acid mist escapes during the charging process of the traditional electrolyte, corrodes the equipment and pollutes the air, long-term inhalation harms human health; poor stability, sulfuric acid in the traditional electrolyte is easy to have side reactions with grid alloy, diaphragm and other materials, which accelerates corrosion and material degradation. SUMMARY

[0005] In order to improve the above problems, reduce the poor safety, serious pollution and poor stability of the electrolyte in the related technology, the present application provides an electrolyte based on acidic ionic liquid and a preparation method thereof, to solve the problems proposed in the above background technology.

[0006] To achieve the above purpose, the present application provides the following technical scheme: An electrolyte based on acidic ionic liquid and a preparation method thereof, comprising the following steps: S1, 1-vinyl-3-(3-sulfopropyl)imidazole is mixed with concentrated sulfuric acid and placed in a Schlenk tube; under the condition of continuously passing nitrogen gas at a flow rate of 50 mL / min, stirring at a temperature of 40℃ and a stirring rate of 500 r / min, the reaction is stirred for 4 h; then 10 times the volume of ice acetone solvent is added dropwise, and the product is precipitated; the precipitate is collected by vacuum filtration and transferred to a vacuum drying oven, dried at a temperature of 60℃ and a vacuum degree of 0.1 MPa for 12 h, to obtain an acidic ionic liquid; S2, the acidic ionic liquid obtained in S1 is injected into a polytetrafluoroethylene forming mold and then peroxide is added, followed by ultrasonic dispersion treatment for 30 min, then preheating at a temperature of 70℃ and polymerizing for 2 h, then heating to 85℃, and then polymerizing for 10 h at a constant temperature, and then naturally cooling to room temperature, to obtain a zwitterionic polymer; S3, the zwitterionic polymer obtained in S2 is placed in a dryer, and a sufficient amount of concentrated sulfuric acid is placed at the bottom of the dryer, and the dryer is placed in a constant temperature air drying oven, and heat treated at a temperature of 50℃ for 8 h, to obtain an acidic ionic liquid polymer; S4, titanium dioxide is dispersed in 1 times the volume of sodium hydroxide solution, stirred at a temperature of 80℃ for 1 h, washed with deionized water after centrifugal separation, and finally dried at a temperature of 100℃, to obtain treated titanium dioxide; S5, then zirconium oxide is immersed in 3 times the volume of an ethanol solution containing a silane coupling agent, refluxed and condensed at a temperature of 70℃ for 3 h, the product is centrifugally separated, washed with ethanol and dried, to obtain treated zirconium oxide; S6, the acidic ionic liquid prepared in S1 is dissolved in anhydrous methanol, then the treated titanium dioxide obtained in S4 and the treated zirconium oxide obtained in S5 are added, ball milled at a rotating speed of 400 r / min for 2 h, then poured into a mold, placed in an oven at a temperature of 50℃ for 2 h, and then subjected to thermal polymerization under the same conditions as S2; then hot-pressed at a temperature of 80℃ and a pressure of 10 MPa for 5 min, cooled and demolded, to obtain an acidic ionic liquid-based electrolyte.

[0007] Preferably, the preparation raw materials of the acidic ionic liquid-based electrolyte each component and the weight fraction are as follows: 1-vinyl-3-(3-sulfopropyl)imidazole 100 parts, concentrated sulfuric acid 53-60 parts, dibenzoyl peroxide 0.25-0.8 parts, titanium dioxide 5-20 parts, and zirconium oxide 1.5-20 parts.

[0008] Preferably, the mass concentration of the concentrated sulfuric acid in S1 is 98%.

[0009] Preferably, the concentration of the sodium hydroxide solution in S4 is 1 mol / L.

[0010] Preferably, the silane coupling agent in S5 is 3-phosphonopropyltriethoxysilane.

[0011] Preferably, the amount of silane coupling agent in S5 is 2% of the mass of zirconium oxide.

[0012] Preferably, the acid ionic liquid in S6 needs to be dissolved in anhydrous methanol to prepare a solution with a mass concentration of 80%.

[0013] Preferably, the deionized water washing in S4 needs to be repeatedly washed with deionized water until the filtrate is neutral.

[0014] The application directly converts the flowing liquid precursor into a quasi-solid polymer electrolyte matrix with a three-dimensional network structure by in-situ thermal initiation polymerization of the polymerizable acid ionic liquid monomer, constructs a high-strength bulk structure, and improves the safety of the electrolyte; The application utilizes the rich sulfonate groups in the zwitterionic polymer skeleton to react with concentrated sulfuric acid to form a strong acid ion pair with strong interaction and chemically immobilize it on the polymer network, stably anchors the high-concentration proton conduction sites, and greatly improves the environmental friendliness; The application introduces a metal oxide with differential surface treatment, constructs a biphasic continuous interpenetrating network in the polymer matrix by means of electrostatic interaction and interface design, simultaneously provides a fast interface ion transmission channel and a strong mechanical support skeleton, significantly enhances the material's resistance to chemical corrosion and physical deformation, and improves the stability of the electrolyte. DETAILED DESCRIPTION

[0015] The application will be further described in detail below in combination with the examples of the application. The raw materials used in the examples and embodiments of the application are all common commercially available materials, except for the special descriptions below. Preparation Examples 1-5 An electrolyte based on an acid ionic liquid is prepared by using the preparation components and their corresponding ratios shown in the following table and by using the following preparation method: S1, mix 1-vinyl-3-(3-sulfopropyl) imidazole with concentrated sulfuric acid and place it in a Schlenk tube; under the condition of continuously introducing nitrogen gas at a flow rate of 50 mL / min, stirring at a temperature of 40℃ and a stirring rate of 500 r / min, stir for 4h; then drop 10 times the volume of ice acetone solvent, and wait for the product to precipitate; collect the precipitate by vacuum filtration, and transfer it to a vacuum drying oven, dry at a temperature of 60℃ and a vacuum degree of 0.1 MPa for 12 hours to obtain an acid ionic liquid; The mass concentration of the concentrated sulfuric acid is 98%; S2, the acid ionic liquid obtained in S1 was injected into a polytetrafluoroethylene forming mold and dibenzoyl peroxide was added, and then ultrasonic dispersion treatment was performed for 30 min, followed by preheating at a temperature of 70℃ and polymerization for 2h, then the temperature was increased to 85℃, and after constant temperature polymerization reaction for 10h, it was naturally cooled to room temperature to obtain a zwitterionic polymer; S3, the zwitterionic polymer obtained in S2 was placed in a desiccator, and a sufficient amount of concentrated sulfuric acid was placed at the bottom of the desiccator, and the desiccator was placed in a constant temperature air drying oven and heat treated at a temperature of 50℃ for 8h to obtain an acid ionic liquid polymer; S4, titanium dioxide was dispersed in 1 times volume of sodium hydroxide solution, stirred at a temperature of 80℃ for 1h, washed with deionized water repeatedly until the filtrate was neutral after centrifugal separation, and finally dried at a temperature of 100℃ to obtain treated titanium dioxide; The concentration of the sodium hydroxide solution is 1 mol / L; S5, then the zirconium oxide was immersed in 3 times volume of ethanol solution containing silane coupling agent, and refluxed and condensed at a temperature of 70℃ for 3h, the product was centrifuged, washed with ethanol and dried to obtain treated zirconium oxide; The silane coupling agent is 3-phosphonopropyltriethoxysilane; The amount of silane coupling agent is 2% of the mass of zirconium oxide; S6, the acid ionic liquid prepared in S1 was dissolved in anhydrous methanol, then the treated titanium dioxide obtained in S4 and the treated zirconium oxide obtained in S5 were added, and ball milling treatment was performed at a rotation speed of 400r / min for 2h, then it was poured into a mold and placed in an oven at a temperature of 50℃ for 2h, then heat polymerization reaction was performed under the same conditions as S2; followed by hot pressing at a temperature of 80℃ and a pressure of 10MPa for 5min, and after cooling, the mold was removed to obtain an acid ionic liquid-based electrolyte.

[0016] The acid ionic liquid is dissolved in anhydrous methanol to prepare a solution with a mass concentration of 80%; Table: mass ratio (g) of each component of raw materials in preparation examples 1-5 Preparation Example 6 An acid ionic liquid-based electrolyte, different from preparation example 1, is prepared as follows: S1, 1-vinyl-3-(3-sulfopropyl)imidazole was mixed with concentrated sulfuric acid and placed in a Schlenk tube; under the condition of continuously passing nitrogen gas at a flow rate of 50 mL / min, stirring at a temperature of 30℃ and a stirring rate of 200 r / min, the reaction was stirred for 2 h; then 10 times the volume of ice acetone solvent was added dropwise, and the product was precipitated; the precipitate was collected by vacuum filtration and transferred to a vacuum drying oven, dried at a temperature of 60℃ and a vacuum degree of 0.1 MPa for 12 hours, to obtain an acidic ionic liquid; S2, the acidic ionic liquid obtained in S1 was injected into a polytetrafluoroethylene forming mold and di benzoyl peroxide was added, then ultrasonic dispersion treatment was carried out for 30 min, then preheating was carried out at a temperature of 70℃ and polymerization was carried out for 2 h, then the temperature was raised to 85℃, and after isothermal polymerization reaction for 10 h, it was naturally cooled to room temperature, to obtain a zwitterionic polymer; S3, the zwitterionic polymer obtained in S2 was placed in a desiccator, and sufficient concentrated sulfuric acid was placed at the bottom of the desiccator, and the desiccator was placed in a constant temperature air drying oven, and heat treated at a temperature of 50℃ for 8 h, to obtain an acidic ionic liquid polymer; S4, titanium dioxide was dispersed in 1 times the volume of sodium hydroxide solution, stirred at a temperature of 80℃ for 1 h, washed with deionized water repeatedly after centrifugal separation until the filtrate was neutral, and finally dried at a temperature of 100℃, to obtain treated titanium dioxide; S5, then zirconium oxide was immersed in 3 times the volume of ethanol solution containing silane coupling agent, refluxed and condensed at a temperature of 70℃ for 3 h, and the product was washed with ethanol and dried after centrifugal separation, to obtain treated zirconium oxide; S6, the acidic ionic liquid prepared in S1 was dissolved in anhydrous methanol, then the treated titanium dioxide obtained in S4 and the treated zirconium oxide obtained in S5 were added, and ball milling treatment was carried out at a rotating speed of 400 r / min for 2 h, then poured into a mold and placed in an oven at a temperature of 50℃ for 2 h, and then heat polymerization reaction was carried out under the same conditions as S2; then hot-pressed at a temperature of 80℃ and a pressure of 10 MPa for 5 min, and demolded after cooling, to obtain an electrolyte based on acidic ionic liquid.

[0017] Preparation Example 7 An electrolyte based on acidic ionic liquid, which is different from Preparation Example 1 in that the preparation method is as follows: S1, 1-vinyl-3-(3-sulfopropyl)imidazole was mixed with concentrated sulfuric acid and placed in a Schlenk tube; under the condition of continuously passing nitrogen gas at a flow rate of 50 mL / min, stirring at a temperature of 60℃ and a stirring rate of 600 r / min, the reaction was stirred for 6 h; then 10 times the volume of ice acetone solvent was added dropwise, and the product was precipitated; the precipitate was collected by vacuum filtration and transferred to a vacuum drying oven, dried at a temperature of 60℃ and a vacuum degree of 0.1 MPa for 12 hours, to obtain an acidic ionic liquid; S2, the acidic ionic liquid obtained in S1 was injected into a polytetrafluoroethylene forming mold and di benzoyl peroxide was added, then ultrasonic dispersion treatment was carried out for 30 min, then preheating was carried out at a temperature of 70℃ and polymerization was carried out for 2 h, then the temperature was raised to 85℃, and after isothermal polymerization reaction for 10 h, it was naturally cooled to room temperature, to obtain a zwitterionic polymer; S3, the zwitterionic polymer obtained in S2 was placed in a desiccator, and sufficient concentrated sulfuric acid was placed at the bottom of the desiccator, and the desiccator was placed in a constant temperature air drying oven, and heat treated at a temperature of 50℃ for 8 h, to obtain an acidic ionic liquid polymer; S4, titanium dioxide was dispersed in 1 times the volume of sodium hydroxide solution, stirred at a temperature of 80℃ for 1 h, washed with deionized water repeatedly after centrifugal separation until the filtrate was neutral, and finally dried at a temperature of 100℃, to obtain treated titanium dioxide; S5, then zirconium oxide was immersed in 3 times the volume of ethanol solution containing silane coupling agent, refluxed and condensed at a temperature of 70℃ for 3 h, and the product was washed with ethanol and dried after centrifugal separation, to obtain treated zirconium oxide; S6, the acidic ionic liquid prepared in S1 was dissolved in anhydrous methanol, then the treated titanium dioxide obtained in S4 and the treated zirconium oxide obtained in S5 were added, and ball milling treatment was carried out at a rotating speed of 400 r / min for 2 h, then poured into a mold and placed in an oven at a temperature of 50℃ for 2 h, and then heat polymerization reaction was carried out under the same conditions as S2; then hot-pressed at a temperature of 80℃ and a pressure of 10 MPa for 5 min, and demolded after cooling, to obtain an electrolyte based on acidic ionic liquid.

[0018] Preparation Example 8 An electrolyte based on acidic ionic liquid, which is different from Preparation Example 1 in that the preparation method is as follows: S1, 1-vinyl-3-(3-sulfopropyl)imidazole was mixed with concentrated sulfuric acid and placed in a Schlenk tube; under the condition of continuously passing nitrogen gas at a flow rate of 50 mL / min, stirring at a temperature of 40℃ and a stirring rate of 500 r / min, the reaction was stirred for 4 h; then 10 times the volume of ice acetone solvent was added dropwise, and the product was precipitated; the precipitate was collected by vacuum filtration and transferred to a vacuum drying oven, dried at a temperature of 60℃ and a vacuum degree of 0.1 MPa for 12 hours, to obtain an acidic ionic liquid; S2, the acidic ionic liquid obtained in S1 was injected into a polytetrafluoroethylene forming mold and di benzoyl peroxide was added, then ultrasonic dispersion treatment was carried out for 30 min, then preheating was carried out at a temperature of 60℃ and polymerization was carried out for 1 h, then the temperature was raised to 75℃, and after constant temperature polymerization reaction for 8 h, natural cooling to room temperature was carried out, to obtain a zwitterionic polymer; S3, the zwitterionic polymer obtained in S2 was placed in a desiccator, and sufficient concentrated sulfuric acid was placed at the bottom of the desiccator, and the desiccator was placed in a constant temperature air drying oven, and heat treatment was carried out at a temperature of 50℃ for 8 h, to obtain an acidic ionic liquid polymer; S4, titanium dioxide was dispersed in 1 times the volume of sodium hydroxide solution, stirred at a temperature of 80℃ for 1 h, washed with deionized water repeatedly after centrifugal separation until the filtrate was neutral, and finally dried at a temperature of 100℃, to obtain treated titanium dioxide; S5, then zirconium oxide was immersed in 3 times the volume of ethanol solution containing silane coupling agent, refluxed and condensed at a temperature of 70℃ for 3 h, the product was centrifugally separated, washed with ethanol and dried, to obtain treated zirconium oxide; S6, the acidic ionic liquid prepared in S1 was dissolved in anhydrous methanol, then the treated titanium dioxide obtained in S4 and the treated zirconium oxide obtained in S5 were added, and ball milling treatment was carried out at a rotating speed of 400 r / min for 2 h, then poured into a mold, placed in an oven at a temperature of 50℃ for 2 h, and then heat polymerization reaction was carried out under the same conditions as S2; then hot pressing was carried out at a temperature of 80℃ and a pressure of 10 MPa for 5 min, and after cooling, demolding was carried out, to obtain an electrolyte based on acidic ionic liquid.

[0019] Preparation Example 9 An electrolyte based on acidic ionic liquid, which is different from Preparation Example 1, is prepared by the following method: S1, 1-vinyl-3-(3-sulfopropyl)imidazole was mixed with concentrated sulfuric acid and placed in a Schlenk tube; under the condition of continuously passing nitrogen gas at a flow rate of 50 mL / min, stirring at a temperature of 40℃ and a stirring rate of 500 r / min, the reaction was stirred for 4 h; then 10 times the volume of ice acetone solvent was added dropwise, and the product was precipitated; the precipitate was collected by vacuum filtration and transferred to a vacuum drying oven, dried at a temperature of 60℃ and a vacuum degree of 0.1 MPa for 12 hours, to obtain an acidic ionic liquid; S2, the acidic ionic liquid obtained in S1 was injected into a polytetrafluoroethylene forming mold and di benzoyl peroxide was added, then ultrasonic dispersion treatment was carried out for 30 min, then preheating was carried out at a temperature of 75℃ and polymerization was carried out for 4 h, then the temperature was raised to 90℃, and after constant temperature polymerization reaction for 24 h, natural cooling to room temperature was carried out, to obtain a zwitterionic polymer; S3, the zwitterionic polymer obtained in S2 was placed in a desiccator, and sufficient concentrated sulfuric acid was placed at the bottom of the desiccator, and the desiccator was placed in a constant temperature air drying oven, and heat treatment was carried out at a temperature of 50℃ for 8 h, to obtain an acidic ionic liquid polymer; S4, titanium dioxide was dispersed in 1 times the volume of sodium hydroxide solution, stirred at a temperature of 80℃ for 1 h, washed with deionized water repeatedly after centrifugal separation until the filtrate was neutral, and finally dried at a temperature of 100℃, to obtain treated titanium dioxide; S5, then zirconium oxide was immersed in 3 times the volume of ethanol solution containing silane coupling agent, refluxed and condensed at a temperature of 70℃ for 3 h, the product was centrifugally separated, washed with ethanol and dried, to obtain treated zirconium oxide; S6, the acidic ionic liquid prepared in S1 was dissolved in anhydrous methanol, then the treated titanium dioxide obtained in S4 and the treated zirconium oxide obtained in S5 were added, ball milling was carried out at a rotating speed of 400 r / min for 2 h, then poured into a mold, placed in an oven at a temperature of 50℃ for 2 h, and then heat polymerization reaction was carried out under the same conditions as S2; then hot pressing was carried out at a temperature of 80℃ and a pressure of 10 MPa for 5 min, cooled and demolded, to obtain an electrolyte based on acidic ionic liquid.

[0020] Preparation Example 10 An electrolyte based on acidic ionic liquid, different from Preparation Example 1, the preparation method is as follows: S1, 1-vinyl-3-(3-sulfopropyl)imidazole was mixed with concentrated sulfuric acid and placed in a Schlenk tube; under the condition of continuously passing nitrogen gas at a flow rate of 50 mL / min, stirring at a temperature of 40℃ and a stirring rate of 500 r / min, the reaction was stirred for 4 h; then 10 times the volume of ice acetone solvent was added dropwise, and the product was precipitated; the precipitate was collected by vacuum filtration and transferred to a vacuum drying oven, dried at a temperature of 60℃ and a vacuum degree of 0.1 MPa for 12 hours, to obtain an acidic ionic liquid; S2, the acidic ionic liquid obtained in S1 was injected into a polytetrafluoroethylene forming mold and di benzoyl peroxide was added, then ultrasonic dispersion treatment was carried out for 30 min, then preheating was carried out at a temperature of 70℃ and polymerization was carried out for 2 h, then the temperature was raised to 85℃, and after isothermal polymerization reaction for 10 h, it was naturally cooled to room temperature, to obtain a zwitterionic polymer; S3, the zwitterionic polymer obtained in S2 was placed in a desiccator, and sufficient concentrated sulfuric acid was placed at the bottom of the desiccator, and the desiccator was placed in a constant temperature air drying oven, and heat treated at a temperature of 40℃ for 4 h, to obtain an acidic ionic liquid polymer; S4, titanium dioxide was dispersed in 1 times the volume of sodium hydroxide solution, stirred at a temperature of 80℃ for 1 h, washed with deionized water repeatedly after centrifugal separation until the filtrate was neutral, and finally dried at a temperature of 100℃, to obtain treated titanium dioxide; S5, then zirconium oxide was immersed in 3 times the volume of ethanol solution containing silane coupling agent, refluxed and condensed at a temperature of 70℃ for 3 h, and the product was washed with ethanol and dried after centrifugal separation, to obtain treated zirconium oxide; S6, the acidic ionic liquid prepared in S1 was dissolved in anhydrous methanol, then the treated titanium dioxide obtained in S4 and the treated zirconium oxide obtained in S5 were added, and ball milling treatment was carried out at a rotating speed of 400 r / min for 2 h, then poured into a mold and placed in an oven at a temperature of 50℃ for 2 h, and then heat polymerization reaction was carried out under the same conditions as S2; then hot-pressed at a temperature of 80℃ and a pressure of 10 MPa for 5 min, and demolded after cooling, to obtain an electrolyte based on acidic ionic liquid.

[0021] Preparation Example 11 An electrolyte based on acidic ionic liquid, which is different from Preparation Example 1 in that the preparation method is as follows: S1, 1-vinyl-3-(3-sulfopropyl)imidazole was mixed with concentrated sulfuric acid and placed in a Schlenk tube; under the condition of continuously passing nitrogen gas at a flow rate of 50 mL / min, stirring at a temperature of 40℃ and a stirring rate of 500 r / min, the reaction was stirred for 4 h; then 10 times the volume of ice acetone solvent was added dropwise, and the product was precipitated; the precipitate was collected by vacuum filtration and transferred to a vacuum drying oven, dried at a temperature of 60℃ and a vacuum degree of 0.1 MPa for 12 hours, to obtain an acidic ionic liquid; S2, the acidic ionic liquid obtained in S1 was injected into a polytetrafluoroethylene forming mold and di benzoyl peroxide was added, then ultrasonic dispersion treatment was carried out for 30 min, then preheating was carried out at a temperature of 70℃ and polymerization was carried out for 2 h, then the temperature was raised to 85℃, and after isothermal polymerization reaction for 10 h, it was naturally cooled to room temperature, to obtain a zwitterionic polymer; S3, the zwitterionic polymer obtained in S2 was placed in a desiccator, and sufficient concentrated sulfuric acid was placed at the bottom of the desiccator, and the desiccator was placed in a constant temperature air drying oven, and heat treated at a temperature of 70℃ for 12 h, to obtain an acidic ionic liquid polymer; S4, titanium dioxide was dispersed in 1 times the volume of sodium hydroxide solution, stirred at a temperature of 80℃ for 1 h, washed with deionized water repeatedly after centrifugal separation until the filtrate was neutral, and finally dried at a temperature of 100℃, to obtain treated titanium dioxide; S5, then zirconium oxide was immersed in 3 times the volume of ethanol solution containing silane coupling agent, refluxed and condensed at a temperature of 70℃ for 3 h, and the product was washed with ethanol and dried after centrifugal separation, to obtain treated zirconium oxide; S6, the acidic ionic liquid prepared in S1 was dissolved in anhydrous methanol, then the treated titanium dioxide obtained in S4 and the treated zirconium oxide obtained in S5 were added, and ball milling treatment was carried out at a rotating speed of 400 r / min for 2 h, then poured into a mold and placed in an oven at a temperature of 50℃ for 2 h, and then heat polymerization reaction was carried out under the same conditions as S2; then hot-pressed at a temperature of 80℃ and a pressure of 10 MPa for 5 min, and demolded after cooling, to obtain an electrolyte based on acidic ionic liquid.

[0022] Preparation Example 12 An electrolyte based on acidic ionic liquid, which is different from Preparation Example 1 in that the preparation method is as follows: S1, 1-vinyl-3-(3-sulfopropyl)imidazole was mixed with concentrated sulfuric acid and placed in a Schlenk tube; under the condition of continuously passing nitrogen gas at a flow rate of 50 mL / min, stirring at a temperature of 40℃ and a stirring rate of 500 r / min, the reaction was stirred for 4 h; then 10 times the volume of ice acetone solvent was added dropwise, and the product was precipitated; the precipitate was collected by vacuum filtration and transferred to a vacuum drying oven, dried at a temperature of 60℃ and a vacuum degree of 0.1 MPa for 12 hours, to obtain an acidic ionic liquid; S2, the acidic ionic liquid obtained in S1 was injected into a polytetrafluoroethylene forming mold and di benzoyl peroxide was added, then ultrasonic dispersion treatment was carried out for 30 min, then preheating was carried out at a temperature of 70℃ and polymerization was carried out for 2 h, then the temperature was raised to 85℃, and after isothermal polymerization reaction for 10 h, it was naturally cooled to room temperature, to obtain a zwitterionic polymer; S3, the zwitterionic polymer obtained in S2 was placed in a desiccator, and sufficient concentrated sulfuric acid was placed at the bottom of the desiccator, and the desiccator was placed in a constant temperature air drying oven, and heat treated at a temperature of 50℃ for 8 h, to obtain an acidic ionic liquid polymer; S4, titanium dioxide was dispersed in 1 times the volume of sodium hydroxide solution, stirred at a temperature of 80℃ for 1 h, washed with deionized water repeatedly after centrifugal separation until the filtrate was neutral, and finally dried at a temperature of 100℃, to obtain treated titanium dioxide; S5, then zirconium oxide was immersed in 3 times the volume of ethanol solution containing silane coupling agent, refluxed and condensed at a temperature of 70℃ for 3 h, and the product was washed with ethanol and dried after centrifugal separation, to obtain treated zirconium oxide; S6, the acidic ionic liquid prepared in S1 was dissolved in anhydrous methanol, then the treated titanium dioxide obtained in S4 and the treated zirconium oxide obtained in S5 were added, and ball milling was carried out at a rotating speed of 300 r / min for 1 h, then poured into a mold and placed in an oven at a temperature of 50℃ for 2 h, and then heat polymerization reaction was carried out under the same conditions as S2; then hot-pressed at a temperature of 70℃ and a pressure of 5 MPa for 3 min, and demolded after cooling, to obtain an electrolyte based on acidic ionic liquid.

[0023] Preparation Example 13 An electrolyte based on acidic ionic liquid, which is different from Preparation Example 1 in that the preparation method is as follows: S1, 1-vinyl-3-(3-sulfopropyl)imidazole was mixed with concentrated sulfuric acid and placed in a Schlenk tube; under the condition of continuously passing nitrogen at a flow rate of 50 mL / min, stirring at a speed of 500 r / min, the reaction was stirred at a temperature of 40℃ for 4h; then 10 times the volume of ice acetone solvent was added dropwise, and the product was precipitated; the precipitate was collected by vacuum filtration and transferred to a vacuum drying oven, dried at a temperature of 60℃ under a vacuum of 0.1 MPa for 12 hours, to obtain an acidic ionic liquid; S2, the acidic ionic liquid obtained in S1 was injected into a polytetrafluoroethylene forming mold and di benzoyl peroxide was added, then ultrasonic dispersion treatment was carried out for 30 min, then preheating was carried out at a temperature of 70℃ and polymerization was carried out for 2h, then the temperature was raised to 85℃, and after constant temperature polymerization reaction for 10h, it was naturally cooled to room temperature, to obtain a zwitterionic polymer; S3, the zwitterionic polymer obtained in S2 was placed in a desiccator, and sufficient concentrated sulfuric acid was placed at the bottom of the desiccator, and the desiccator was placed in a constant temperature air drying oven and heat treated at a temperature of 50℃ for 8h, to obtain an acidic ionic liquid polymer; S4, titanium dioxide was dispersed in 1 times the volume of sodium hydroxide solution, stirred at a temperature of 80℃ for 1h, after centrifugal separation, deionized water was repeatedly washed until the filtrate was neutral, and finally dried at a temperature of 100℃, to obtain treated titanium dioxide; S5, then zirconium oxide was immersed in 3 times the volume of ethanol solution containing silane coupling agent, refluxed and condensed under stirring at a temperature of 70℃ for 3h, the product was centrifugally separated, washed with ethanol and dried, to obtain treated zirconium oxide; S6, the acidic ionic liquid prepared in S1 was dissolved in anhydrous methanol, then the treated titanium dioxide obtained in S4 and the treated zirconium oxide obtained in S5 were added, and ball milling was carried out at a speed of 600 r / min for 4h, then poured into a mold and placed in an oven at a temperature of 50℃ for 2h, then heat polymerization reaction was carried out under the same conditions as S2; then heat pressing was carried out at a temperature of 100℃ and a pressure of 20 MPa for 15 min, and after cooling, demolding was carried out, to obtain an electrolyte based on acidic ionic liquid.

[0024] Performance detection test The electrolyte based on acidic ionic liquid prepared in each embodiment was selected for testing, and the test objects were 130 portions of electrolyte based on acidic ionic liquid, 10 portions in each group; the safety, environmental protection, stability and electrochemical performance were detected, and the specific detection steps were as follows: Safety: First, the acid ionic liquid-based electrolyte prepared in the examples is sampled, and the electrolyte is placed in an 80°C oven for 168 h. The mass change is accurately weighed, and the mass loss rate is calculated by weighing to characterize the safety of the acid ionic liquid-based electrolyte; the test results and evaluation criteria are as follows: Mass loss rate ≤ 1% (considered to be high in safety); Mass loss rate > 1% (considered to be low in safety).

[0025] Environmental friendliness: First, the acid ionic liquid-based electrolyte prepared in the examples is sampled, and then placed in a headspace bottle at 80°C for 24 h. The headspace gas is analyzed using a gas chromatograph-mass spectrometer, the main VOC components are quantified, and the VOC release amount is calculated to characterize the environmental friendliness of the acid ionic liquid-based electrolyte; the test results and evaluation criteria are as follows: VOC release amount < 50 μg / g (considered to be strong in environmental friendliness); VOC release amount > 50 μg / g (considered to be weak in environmental friendliness).

[0026] Stability: First, the acid ionic liquid-based electrolyte prepared in the examples is sampled, and the electrolyte is immersed in a 3 mol / L solution and a 2 mol / L NaOH solution at 60°C for 168 h, and the mass change rate is calculated; to characterize the stability of the acid ionic liquid-based electrolyte; the test results and evaluation criteria are as follows: Mass change rate < 5% (considered to be strong in stability); Mass change rate > 5% (considered to be weak in stability).

[0027] Electrochemical property: First, the acid ionic liquid-based electrolyte prepared in the examples is sampled, and the ionic conductivity at room temperature is calculated using electrochemical impedance spectroscopy; to characterize the electrochemical property of the acid ionic liquid-based electrolyte; the test results and evaluation criteria are as follows: Ionic conductivity ≥ S / cm (considered to be strong in electrochemical property); Ionic conductivity < 0.1 S / cm (considered to be weak in electrochemical property). S / cm (considered to be weak in electrochemical property).

[0028] It should be specifically noted that the above-mentioned acid ionic liquid-based electrolyte is an acid ionic liquid-based electrolyte produced in a normal production mode, and a defective acid ionic liquid-based electrolyte produced. The data of the acid ionic liquid-based electrolyte is discarded.

[0029] Examples 1-5 An electrolyte based on an acidic ionic liquid, and a method for preparing the same, are provided.

[0030] Table: Comparison of the use of the electrolyte based on an acidic ionic liquid in Examples 1-5 The electrolyte based on an acidic ionic liquid in the above Examples 1-5 was extracted, and its mass loss rate, VOC emission, mass change rate, and ionic conductivity were measured according to the above measurement steps and standards, and the average values of the test results are shown in the following table.

[0031] Table: Performance test results of the mass loss rate, VOC emission, mass change rate, and ionic conductivity of Examples 1-5 As can be seen from the above table, the electrolyte based on acidic ionic liquid in the preparation process of examples 1-5 has good effect of improving the production effect of electrolyte based on acidic ionic liquid, 1-vinyl-3-(3-sulfopropyl) imidazole as the core functional monomer, the vinyl group in its molecular structure provides a polymerizable site, which can form a three-dimensional polymer skeleton through free radical polymerization, providing structural support and dimensional stability for the electrolyte, and improving its safety; At the same time, the sulfopropyl group on the side chain becomes a fixed site for proton transmission after subsequent acidification, which is the chemical basis of ion conduction function; Concentrated sulfuric acid reacts with sulfonate groups in the monomer to form sulfonic acid through protonation and further form stable acidic ion pairs with bisulfate, which chemically immobilizes the strong acid component on the polymer skeleton, which not only provides a high concentration of mobile protons to achieve high ionic conductivity, but also completely eliminates the corrosiveness and volatility of free strong acid, significantly improving environmental friendliness and operation safety; Diphenyl peroxide as a thermal initiator, through thermal decomposition to produce free radicals to initiate monomer polymerization, its amount accurately controls the crosslinking density and molecular chain length of the polymer network, and moderate crosslinking can obtain a substrate with good mechanical strength and flexibility, which provides mechanical stability against deformation for the electrolyte and ensures the formation of a stable contact interface with the electrode; Titanium dioxide as a functional filler, its surface is rich in hydroxyl groups after alkaline treatment, which is easy to interact with proton species in the polymer to form a fast interface proton transmission channel, and its nanowire form is more likely to build a continuous ion conduction network in the substrate, thereby directly improving the overall conductivity and electrochemical reaction speed of the electrolyte. Zirconium oxide nanoparticles as reinforcing fillers, after surface modification by phosphoric acid, the phosphate groups on their surface can form strong hydrogen bond interactions with the polymer matrix, greatly improving the compatibility and binding force of the inorganic-organic two-phase interface, and their high hardness and thermal stability serve as physical crosslinking points to significantly enhance the mechanical strength, dimensional stability and thermal stability of the electrolyte, preventing cracks or deformation during battery cycling, ensuring the safety and reliability of long-term use; Thus, the purpose of improving the production effect of electrolyte based on acidic ionic liquid is achieved. The mass loss rate is 0.2-0.7%, which is considered to be high in safety; The VOC release amount is 20-38 µg / g, which is considered to be strong in environmental friendliness, the mass change rate is 1.3-4.4%, which is considered to be strong in stability, the ionic conductivity is S / cm, which is considered to be strong in electrochemical performance; It can be seen that when the production raw materials are certain, the production effect of the electrolyte based on the acidic ionic liquid can be increased by adjusting the preparation raw material ratio. It is not difficult to see from the above table data that when the electrolyte based on the acidic ionic liquid is prepared, the electrolyte based on the acidic ionic liquid prepared by using 100 parts of 1-vinyl-3-(3-sulfopropyl) imidazole, 53 parts of concentrated sulfuric acid, 0.25 parts of dibenzoyl peroxide, 5 parts of titanium dioxide and 10 parts of zirconium oxide has the strongest safety. The reason for analyzing is that by using extremely low amount of initiator to build a high toughness polymer network, slightly under-acidic ratio to inhibit harmful side reactions and introduce physical crosslinking to enhance the mechanical properties and interface stability of the main type of filler; by reducing the amount of initiator to an extremely low level, the formation of a flexible polymer network with extremely high molecular weight and low crosslinking density is promoted, so that the electrolyte matrix can effectively release thermal stress at high temperature through chain segment motion, thereby avoiding structural damage and mass loss caused by brittle fracture; at the same time, the proportion of concentrated sulfuric acid is slightly lower than the stoichiometric ratio, which on the one hand reduces the overall acidity of the system, inhibits small molecule side reactions and volatilization that may be caused by strong acid environment, and on the other hand makes part of the unprotonated sulfonate group become a physical crosslinking point to enhance the toughness of the network; in addition, the inorganic filler mainly used to improve the mechanical enhancement of nano zirconium oxide in the formula forms a strong interfacial interaction with the polymer matrix after being modified by phosphoric acid, which not only significantly improves the overall mechanical strength of the composite material, but also prevents defects caused by interfacial debonding during thermal aging as an effective stress buffer point, obtained from examples 1-5; It can be seen that when the production raw materials are certain, the production effect of the electrolyte based on the acidic ionic liquid can be increased by adjusting the preparation raw material ratio. It is not difficult to see from the above table data that when the electrolyte based on the acidic ionic liquid is prepared, the electrolyte based on the acidic ionic liquid prepared by using 100 parts of 1-vinyl-3-(3-sulfopropyl) imidazole, 53 parts of concentrated sulfuric acid, 0.25 parts of dibenzoyl peroxide, 5 parts of titanium dioxide and 10 parts of zirconium oxide has the strongest safety. The reason for analyzing is that by using extremely low amount of initiator to build a high toughness polymer network, slightly under-acidic ratio to inhibit harmful side reactions and introduce physical crosslinking to enhance the mechanical properties and interface stability of the main type of filler; by reducing the amount of initiator to an extremely low level, the formation of a flexible polymer network with extremely high molecular weight and low crosslinking density is promoted, so that the electrolyte matrix can effectively release thermal stress at high temperature through chain segment motion, thereby avoiding structural damage and mass loss caused by brittle fracture; at the same time, the proportion of concentrated sulfuric acid is slightly lower than the stoichiometric ratio, which on the one hand reduces the overall acidity of the system, inhibits small molecule side reactions and volatilization that may be caused by strong acid environment, and on the other hand makes part of the unprotonated sulfonate group become a physical crosslinking point to enhance the toughness of the network; in addition, the inorganic filler mainly used to improve the mechanical enhancement of nano zirconium oxide in the formula forms a strong interfacial interaction with the polymer matrix after being modified by phosphoric acid, which not only significantly improves the overall mechanical strength of the composite material, but also prevents defects caused by interfacial debonding during thermal aging as an effective stress buffer point, obtained from examples 1-5;

[0032] It can be seen that when the production raw materials are certain, the production effect of the electrolyte based on the acidic ionic liquid can be increased by adjusting the preparation raw material ratio. It is not difficult to see from the above table data that when the electrolyte based on the acidic ionic liquid is prepared, the electrolyte based on the acidic ionic liquid prepared by using 100 parts of 1-vinyl-3-(3-sulfopropyl) imidazole, 55 parts of concentrated sulfuric acid, 0.4 parts of dibenzoyl peroxide, 13.5 parts of titanium dioxide and 1.5 parts of zirconium oxide has the strongest electrochemical performance. The reason for analyzing is that by moderately reducing the amount of initiator, a polymer network with longer molecular chain and lower crosslinking density is formed, which provides a more unobstructed and low-resistance matrix environment for ion migration, while maintaining the precise stoichiometric acid ratio, ensuring that each sulfonate group is fully protonated and forms a high-density stable acidic ion pair, thereby maximizing the concentration and activity of movable protons at the molecular level. By increasing the proportion of titanium dioxide as an ion conduction functional filler, it can construct a highly connected and uniformly distributed rapid ion transport channel network in the composite system. These surface-treated nanowires produce strong interfacial interaction with the proton carriers in the polymer through their abundant surface hydroxyl groups, greatly optimizing and accelerating the interface proton hopping and migration process. Reducing the content of mechanical reinforcing filler to a minimum effectively reduces the non-conductive obstacles and tortuosity in the ion transport path, which significantly reduces the overall ion migration resistance of the electrolyte. The results obtained from Examples 1-5 Examples 6-13 An electrolyte based on an acidic ionic liquid, the corresponding relationship of the preparation method used is shown in the following table.

[0033] Table: Use of electrolyte based on acidic ionic liquid in Examples 6-13 Extract the electrolyte based on the acidic ionic liquid in the above Examples 6-13, test its mass loss rate, VOC release amount, mass change rate and ionic conductivity according to the above measurement steps and measurement standards, and the test results are averaged and recorded in the table below.

[0034] Table: Performance test results of mass loss rate, VOC release amount, mass change rate and ionic conductivity of Examples 1, 6-13 As can be seen from the above table, the electrolyte based on acidic ionic liquid in the preparation process of examples 1-5 has good effect of improving the production effect of electrolyte based on acidic ionic liquid, 1-vinyl-3-(3-sulfopropyl) imidazole as the core functional monomer, the vinyl group in its molecular structure provides a polymerizable site, which can form a three-dimensional polymer skeleton through free radical polymerization, providing structural support and dimensional stability for the electrolyte, and improving its safety; At the same time, the sulfopropyl group on the side chain becomes a fixed site for proton transmission after subsequent acidification, which is the chemical basis of ion conduction function; Concentrated sulfuric acid reacts with sulfonate groups in the monomer to form sulfonic acid through protonation and further form stable acidic ion pairs with bisulfate, which chemically immobilizes the strong acid component on the polymer skeleton, which not only provides a high concentration of mobile protons to achieve high ionic conductivity, but also completely eliminates the corrosiveness and volatility of free strong acid, significantly improving environmental friendliness and operation safety; Diphenyl peroxide as a thermal initiator, through thermal decomposition to produce free radicals to initiate monomer polymerization, its dosage accurately controls the crosslinking density and molecular chain length of the polymer network, and moderate crosslinking can obtain a substrate with good mechanical strength and flexibility, which provides mechanical stability against deformation for the electrolyte and ensures the formation of a stable contact interface with the electrode; Titanium dioxide as a functional filler, its surface is rich in hydroxyl groups after alkaline treatment, which is easy to interact with proton species in the polymer to form a fast interface proton transmission channel, and its nanowire form is more likely to build a continuous ion conduction network in the substrate, thereby directly improving the overall conductivity and electrochemical reaction speed of the electrolyte. Zirconium oxide nanoparticles as reinforcing fillers, after surface modification by phosphoric acid, the phosphate groups on their surface can form strong hydrogen bond interactions with the polymer matrix, greatly improving the compatibility and binding force of the inorganic-organic two-phase interface, and their high hardness and thermal stability serve as physical crosslinking points to significantly enhance the mechanical strength, dimensional stability and thermal stability of the electrolyte, preventing cracks or deformation during battery cycling, ensuring the safety and reliability of long-term use; Thus, the purpose of improving the production effect of electrolyte based on acidic ionic liquid is achieved. The mass loss rate is 0.5-0.9%, which is considered to be high in safety; The VOC release amount is 35-43 µg / g, which is considered to be strong in environmental friendliness, the mass change rate is 3-4%, which is considered to be strong in stability, and the ionic conductivity is S / cm, which is considered to be strong in electrochemical performance; It can be seen that when the production raw materials are certain, the production effect of the electrolyte based on the acidic ionic liquid can be increased by adjusting the preparation conditions. It is not difficult to see from the data in the above table that when the electrolyte based on the acidic ionic liquid is prepared, the acidic ionic liquid is synthesized under the condition of a temperature of 40℃, a stirring rate of 500r / min and stirring for 4h; the polymerization reaction is preheated and polymerized at a temperature of 70℃ for 2h, and then heated to 85℃, and the polymerization reaction is carried out at a constant temperature for 10h; the acidic ionic liquid polymer is heat-treated at a temperature of 50℃ for 8h; the ball milling process is carried out at a speed of 400r / min for 2h; and the electrolyte is hot-pressed at a temperature of 80℃ and a pressure of 10MPa for 5min. The electrolyte based on the acidic ionic liquid prepared has the maximum safety, environmental protection, stability and electrochemical property. The reason is that in the synthesis of the acidic ionic liquid, the temperature, the stirring rate and the reaction time are used to ensure that the protonation and ion pair formation reaction between concentrated sulfuric acid and sulfonate groups can be completely and uniformly carried out, so that the strong acid component is stably immobilized, the existence of free acid and volatile small molecules is minimized from the source, which directly lays the foundation for high environmental protection and high stability; in the polymerization stage, the step-by-step heating strategy is adopted, the polymerization is initiated at a relatively low temperature to form a preliminary network, and then the temperature is increased to a higher temperature to complete the full polymerization. This method is beneficial to form a polymer skeleton with more uniform molecular weight distribution, fewer defects and moderate flexibility. This structure can effectively embed active substances to reduce high-temperature volatilization and improve safety, and also provides a good polymer matrix for ion transmission. The subsequent low-temperature long-time heat treatment further promotes the orientation arrangement and stabilization of the acidic ion pairs in the polymer network, and enhances the chemical stability of resisting acid and alkali corrosion; in the composite process, sufficient ball milling strength and time ensure the high uniform dispersion of the nano filler in the polymer precursor, and a continuous and interpenetrating organic-inorganic network is constructed, which not only inhibits volatilization and improves safety through the barrier effect of the filler, but also forms an efficient ion conduction channel; finally, the appropriate hot-pressing temperature and pressure make the composite film reach the optimal densification, eliminating internal pores and interface defects, which not only significantly improves the mechanical integrity, resistance to harsh environments and stability, but also ensures the low resistance and high connectivity of the ion transmission path, as shown in Examples 1, 6-13. The specific embodiments are only an explanation of the present application, not a limitation of the present application. Those skilled in the art can make modifications to the embodiments without creative contribution after reading the specification, as long as the modifications are within the scope of the claims of the present application.

Claims

1. A method for preparing an electrolyte based on an acidic ionic liquid, characterized in that, Includes the following steps: S1. Mix 1-vinyl-3-(3-sulfopropyl)imidazolium with concentrated sulfuric acid and place it in a Schran tube; under the condition of continuous nitrogen flow at a flow rate of 50 mL / min, stir the reaction at 40 °C and a stirring rate of 500 r / min for 4 h; then add 10 times the volume of ice-cold acetone solvent, and wait for the product to precipitate; collect the precipitate by vacuum filtration, and transfer it to a vacuum drying oven, and dry it at 60 °C and a vacuum degree of 0.1 MPa for 12 h to obtain an acidic ionic liquid; S2. The acidic ionic liquid obtained in S1 is injected into a polytetrafluoroethylene molding mold and benzoyl peroxide is added. Then, ultrasonic dispersion is performed for 30 minutes. After that, it is preheated at 70°C and polymerized for 2 hours. Then, the temperature is raised to 85°C and the polymerization reaction is carried out at a constant temperature for 10 hours. After that, it is naturally cooled to room temperature to obtain a zwitterionic polymer. S3. Place the zwitterionic polymer obtained in S2 in a desiccator, place sufficient concentrated sulfuric acid at the bottom of the desiccator, and place the desiccator in a constant temperature forced-air drying oven. Heat treat at 50℃ for 8 hours to obtain an acidic ionic liquid polymer. S4. Disperse titanium dioxide in a sodium hydroxide solution of 1 volume, stir at 80°C for 1 hour, centrifuge, wash with deionized water, and finally dry at 100°C to obtain the treated titanium dioxide. S5. Then, the zirconium oxide is immersed in 3 times its volume of ethanol solution containing silane coupling agent, refluxed and stirred at 70°C for 3 hours. After centrifugation, the product is washed with ethanol and dried to obtain the treated zirconium oxide. S6. Dissolve the acidic ionic liquid prepared in S1 in anhydrous methanol, then add the titanium dioxide treated in S4 and the zirconium oxide treated in S5, and ball mill at 400 r / min for 2 h. Then pour it into a mold and place it in an oven at 50 °C for 2 h. Then carry out a thermal polymerization reaction under the same conditions as in S2. Next, hot press it at 80 °C and 10 MPa for 5 min. After cooling, demold to obtain an electrolyte based on the acidic ionic liquid.

2. The method for preparing an electrolyte based on an acidic ionic liquid according to claim 1, characterized in that: The components and weight proportions of the raw materials for preparing the electrolyte based on acidic ionic liquid are as follows: 100 parts of 1-vinyl-3-(3-sulfopropyl)imidazolium, 53-60 parts of concentrated sulfuric acid, 0.25-0.8 parts of benzoyl peroxide, 5-20 parts of titanium dioxide, and 1.5-20 parts of zirconium oxide.

3. The method for preparing an electrolyte based on an acidic ionic liquid according to claim 1, characterized in that: The mass concentration of concentrated sulfuric acid in S1 is 98%.

4. The method for preparing an electrolyte based on an acidic ionic liquid according to claim 1, characterized in that: The concentration of sodium hydroxide solution in S4 is 1 mol / L.

5. The method for preparing an electrolyte based on an acidic ionic liquid according to claim 1, characterized in that: The silane coupling agent in S5 is propyltriethoxysilane 3-phosphate.

6. The method for preparing an electrolyte based on an acidic ionic liquid according to claim 1, characterized in that: The amount of silane coupling agent used in S5 is 2% of the mass of zirconium oxide.

7. The method for preparing an electrolyte based on an acidic ionic liquid according to claim 1, characterized in that: The acidic ionic liquid in S6 needs to be prepared into a solution with a mass concentration of 80% when dissolved in anhydrous methanol.

8. The method for preparing an electrolyte based on an acidic ionic liquid according to claim 1, characterized in that: In step S4, the deionized water washing process requires repeated washing with deionized water until the filtrate is neutral.

9. An electrolyte based on an acidic ionic liquid prepared by the preparation method according to any one of claims 1-8.

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