WO2018184341A1

WO2018184341A1 - Preparation method for high-performance material for use in supercapacitor

Info

Publication number: WO2018184341A1
Application number: PCT/CN2017/098517
Authority: WO
Inventors: 黄啸谷; 张其土
Original assignee: 苏州海凌达电子科技有限公司
Priority date: 2017-04-07
Filing date: 2017-08-22
Publication date: 2018-10-11
Also published as: CN106847532A

Abstract

Disclosed is a preparation method for a high-performance material for use in a supercapacitor. The process is such that acetylene carbon black, sulfuric acid, and styrene sulfonate are mixed and heated, and then undergo a series of operations such as thermal insulation and cooling to produce a modified carbon black complex, which is then added with dilithium hydrogen phosphate and nickel chloride and reacted in a reaction vessel, treated with an acid and then mixed with a reactant from a high-temperature reaction of raw materials such as acrylonitril powder, distilled water is added for ultrasonic dispersion, dibutyl sebacate, nano-magnesia, antimony trioxide, coconut oleic acid monoethanolamide, and a silane coupling agent are added for a high-temperature reaction, and finally a product is produced via washing and vacuum drying. The high-performance material for use in a supercapacitor has a large specific capacity, great cycle stability, high energy density, great electrical conductivity, and improved application prospect. Also disclosed are applications of the high-performance material prepared per the preparation process and for use in a supercapacitor in the preparation of the supercapacitor.

Description

Method for preparing high performance material for super capacitor

Technical field

The present invention relates to the field of capacitor materials, and more particularly to a method of preparing a high performance material for a supercapacitor.

Background technique

Supercapacitors are energy storage devices between traditional capacitors and batteries. They are widely used in backup power supplies, portable mobile power supplies, hybrid power supplies, etc., and have good application prospects. The utility model has the characteristics of high power of the capacitor, fast charging and discharging, and energy storage characteristics of the electrochemical battery. From the overall structure, supercapacitors are mainly composed of positive and negative electrodes, electrolytes, separators, leads and packaging materials. Supercapacitors are divided into electric double layer capacitors and Faraday quasi-capacitors according to the energy storage mechanism. The energy storage and conversion of electric double layer capacitors is based on the electric double layer theory, and the electric double layer is formed by electrode/electrolyte interface charge separation to realize energy storage. A new type of energy storage device. The performance of a supercapacitor depends primarily on the electrode material on the positive and negative electrode pads. According to the mechanism of storage and conversion of electrical energy, supercapacitors are mainly divided into tantalum capacitor supercapacitors and electric double layer supercapacitors. Tantalum capacitors are energy storage and conversion by electrochemically active substances in the Faraday redox reaction between the electrode surface and the electrolyte. The electrode materials are mainly composed of metal oxides and conductive polymers with larger specific capacitance. Therefore, the tantalum capacitor supercapacitor has a higher energy density, but the conductivity of the electrode material is poor, resulting in poor rate performance and cycle stability of the supercapacitor. The electric double layer supercapacitor stores charge by enriching ions on the electrode. The electrode mainly uses carbon materials such as activated carbon, carbon nanotubes, carbon aerogel and graphene with large specific surface area, and the supercapacitor has better rate performance and cycle performance. . However, the electrode active materials used in the electric double layer supercapacitors generally have a relatively low specific capacitance value and poor electrical conductivity, resulting in a low energy density of the supercapacitor, which limits its development.

Summary of the invention

In order to solve the above technical problems, the present invention provides a method for preparing a high performance material for a supercapacitor, which comprises heating, cooling, diluting, and centrifuging by heating and heating acetylene black and sulfuric acid and sodium styrene sulfonate. After a series of operations such as separation and washing, a modified carbon black composite is obtained, and then lithium dihydrogen phosphate and nickel chloride are added to the reaction vessel for reaction, dried, acid-treated, and then mixed with acrylonitrile powder and dimethyl group. The high temperature reaction reactants such as sulfoxide and tetraethyl orthosilicate are mixed, ultrasonically dispersed by adding distilled water, and dibutyl sebacate, nanometer magnesium oxide, antimony trioxide, coconut oleic acid monoethanolamide, silane coupling agent are added. The high temperature reaction is carried out, and finally, the finished product is obtained by washing and vacuum drying. The high-performance materials prepared for supercapacitors have better specific capacity, good cycle stability, high energy density and good electrical conductivity, and have good application prospects. At the same time, the use of high performance materials for supercapacitors prepared by the preparation process in the preparation of supercapacitors is also disclosed.

The object of the present invention can be achieved by the following technical solutions:

A method for preparing a high performance material for a supercapacitor, comprising the steps of:

(1) 15g of acetylene black is mixed at a liquid-solid ratio of 8-12 with a sulfuric acid having a mass concentration of 92% at 0 ° C, and 3 g of sodium p-styrene sulfonate is added thereto, and heated at a rate of 8-10 ° C / min to raise the temperature. After the temperature is maintained at 110 ° C for 2-3 h, the reaction mixture is cooled to room temperature, 600 mL of distilled water is added to the reaction mixture for dilution, and then centrifuged at 7000-8000 rpm to separate the solution and then use 1000 mL of anhydrous. The lower precipitate obtained by centrifugation is washed 2-3 times with ethanol, and the washed precipitate is added to distilled water to prepare a liquid mixture having a liquid-solid ratio of 15 and transferred to a high-pressure hydrothermal reaction vessel to maintain a volume filling ratio thereof. 1.2, hydrothermal treatment at 350 ° C for 10-15h, after cooling to room temperature, the hydrothermal product is washed and suction filtered until the pH is 7.0-7.2, and then dried in a vacuum oven at a temperature of 75 ° C to a constant weight, Modified carbon black composite;

(2) The modified carbon black composite obtained in the step (1) and 2 g of dilithium hydrogen phosphate were added to distilled water for ultrasonic dispersion at a frequency of 25 KHz for 30 min, then 0.08 g of nickel chloride was added, and stirred at 3000 rpm for 30 min at room temperature. The formed mixture was transferred to a reaction kettle and reacted at 150 ° C for 50 min; after the reaction was completed, the reaction mixture was dried in an oven at 80 ° C overnight to obtain a dried product;

(3) The dried product of the step (2) is subjected to acid treatment with 2.0 mol/L hydrochloric acid, and the liquid-solid ratio of the hydrochloric acid to the dried product is 8-10, the treatment temperature is 55 ° C, and the treatment time is 3-5 h, followed by Deionized water washing and suction filtration until the pH is neutral, and the treated product is dried in a vacuum drying oven at a temperature of 60 ° C for 24 hours to obtain a first dry reactant;

(4) Dissolve 0.6 mg of polyacrylonitrile powder in an appropriate amount of dimethyl sulfoxide, add 100 mL of an aqueous ammonia solution having a concentration of 0.5 mol/L, stir at 70 ° C for 3-5 min at a rate of 200 rpm, and then slowly add 0.5. mL of tetraethyl orthosilicate, then warmed to 100 ° C in a Teflon container, add 10 ml of citric acid solution with a concentration of 0.2 mol / L, continue to raise the temperature to 150 ° C and stir at this temperature for 8-10 h, will get The product was centrifuged at 5000 rpm, and the precipitate was washed with deionized water and dried at 120 ° C to obtain a second dried reactant;

(5) mixing the first dry reactant obtained in the step (3) and the second dry reactant obtained in the step (4), adding to distilled water, sonicating at a frequency of 50 KHz for 45 minutes to obtain a mixed dispersion, and adding 0.5- 0.8 g of dibutyl sebacate, 0.2-0.4 g of nano-magnesia, 0.1-0.3 g of antimony trioxide, 0.06-0.1 g of coconut oleic acid monoethanolamide, 0.05-0.08 g of silane coupling agent, and then raised to 110 ° C The mixture was stirred for 25-30 min. After cooling to room temperature, the reaction solution was filtered to obtain a solid product, which was washed with water and ethanol to neutrality, and then dried in a vacuum oven at 60-70 ° C for 18 h to obtain a high for a supercapacitor. Performance material.

Preferably, the iodine carbon black of the step (1) has an iodine absorption value of 105 g/Kg.

Preferably, in the step (5), 0.6 g of dibutyl sebacate, 0.3 g of nano magnesium oxide, 0.2 g of antimony trioxide, 0.08 g of coconut oleic acid monoethanolamide, and 0.05 g of silane couple are added to the mixed dispersion. Joint agent.

Preferably, the silane coupling agent in the step (5) is selected from the group consisting of vinyl triethoxysilane, methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxy group Any of silanes.

The present invention also provides the use of a high performance material for a supercapacitor obtained by the above-described preparation process in the preparation of a supercapacitor.

Compared with the prior art, the invention has the following beneficial effects:

(1) The high-performance material preparation process for supercapacitor of the present invention is obtained by mixing and heating acetylene black and sulfuric acid, sodium styrene sulfonate, heat preservation, cooling, dilution, centrifugation, washing, and the like. The modified carbon black composite is further reacted with lithium dihydrogen phosphate and nickel chloride in a reaction vessel, dried, and then subjected to acid treatment, and then combined with acrylonitrile powder, dimethyl sulfoxide, tetraethyl orthosilicate, etc. The high-temperature reaction reactants are mixed, ultrasonically dispersed by adding distilled water, and dibutyl sebacate, nano-magnesia oxide, antimony trioxide, coconut oleic acid monoethanolamide, silane coupling agent are added for high-temperature reaction, and finally, washing and vacuum are performed. Dry to get the finished product. The high-performance materials prepared for supercapacitors have better specific capacity, good cycle stability, high energy density and good electrical conductivity, and have good application prospects.

(2) The high-performance material material for the supercapacitor of the present invention is inexpensive, simple in process, and suitable for large-scale industrial use, and has high practicability.

detailed description

The technical solution of the invention will be described in detail below with reference to specific embodiments.

Example 1

(1) 15g of iodine value of 105g / Kg of acetylene black was mixed at a liquid-solid ratio of 8 with a sulfuric acid of 92% by mass at 0 ° C, and 3 g of sodium p-styrenesulfonate was added at a rate of 8 ° C / min. Heating, heating to 110 ° C, the reaction was held for 2 h, then the reaction mixture was cooled to room temperature, 600 mL of distilled water was added to the reaction mixture for dilution, and then centrifuged at 7000 rpm, the solution was separated and removed, and then 1000 mL of absolute ethanol was used. The lower layer precipitate obtained by centrifugation was washed twice, and the washed precipitate was added to distilled water to prepare a liquid-solid ratio mixture of 15 and transferred to a high-pressure hydrothermal reaction vessel to maintain a volume filling ratio of 1.2. After hydrothermal treatment at 350 ° C for 10 h, after cooling to room temperature, the hydrothermal product was washed and suction filtered until the pH was 7.0, and then dried in a vacuum oven at a temperature of 75 ° C to a constant weight to obtain a modified carbon black composite;

(2) The modified carbon black composite obtained in the step (1) and 2 g of dilithium hydrogen phosphate were added to distilled water for ultrasonic dispersion at a frequency of 25 KHz for 30 min, then 0.08 g of nickel chloride was added, and stirred at 3000 rpm for 30 min at room temperature. Will The formed mixture was transferred to a reaction kettle and reacted at 150 ° C for 50 min; after the reaction was completed, the reaction mixture was placed in an oven at 80 ° C to dry overnight to obtain a dried product;

(3) The dried product of the step (2) was subjected to acid treatment with 2.0 mol/L hydrochloric acid, and the liquid-solid ratio of the hydrochloric acid to the dried product was 8, the treatment temperature was 55 ° C, the treatment time was 3 h, and then washed with deionized water. After suction filtration to a neutral pH, the treated product was dried in a vacuum oven at a temperature of 60 ° C for 24 hours to obtain a first dry reactant;

(4) Dissolve 0.6 mg of polyacrylonitrile powder in an appropriate amount of dimethyl sulfoxide, add 100 mL of an aqueous ammonia solution having a concentration of 0.5 mol/L, stir at 70 ° C for 3 min at a rate of 200 rpm, and then slowly add 0.5 mL of positive Ethyl silicate was then heated to 100 ° C in a Teflon vessel, 10 ml of a citric acid solution having a concentration of 0.2 mol/L was added, and the temperature was further raised to 150 ° C and stirred at this temperature for 8 hours, and the obtained product was subjected to 5000 rpm. The rotation speed is centrifuged, the precipitate is washed with deionized water, and dried at 120 ° C to obtain a second dry reactant;

(5) mixing the first dry reactant obtained in the step (3) and the second dry reactant obtained in the step (4), adding it to distilled water, sonicating at a frequency of 50 kHz for 45 minutes to obtain a mixed dispersion, and adding 0.6 g thereto. Dibutyl sebacate, 0.3 g nano-magnesia, 0.2 g antimony trioxide, 0.08 g coconut oleic acid monoethanolamide, 0.05 g vinyl triethoxysilane, then warmed to 110 ° C, stirred with stirring for 25 min, cooled to After the reaction mixture was filtered at room temperature to obtain a solid product, it was washed with water and ethanol to neutrality, and then dried in a vacuum oven at 60 ° C for 18 hours to obtain a high performance material for a supercapacitor.

The performance test results of the obtained high performance materials for supercapacitors are shown in Table 1.

Example 2

(1) 15g of iodine value of 105g / Kg of acetylene black was mixed at a liquid-solid ratio of 10 and 92% of sulfuric acid at 0 ° C, and 3 g of sodium p-styrenesulfonate was added at a rate of 9 ° C / min. Heating, heating to 110 ° C, the reaction was held for 2.5 h, then the reaction mixture was cooled to room temperature, 600 mL of distilled water was added to the reaction mixture for dilution, and then centrifuged at 7500 rpm, the solution was separated and removed, and 1000 mL of water was used. The lower precipitate obtained by centrifugation was washed twice with ethanol, and the washed precipitate was added to distilled water to prepare a liquid mixture having a liquid-solid ratio of 15, and transferred to a high-pressure hydrothermal reaction vessel to maintain a volume filling ratio of 1.2. After hydrothermal treatment at 350 ° C for 12 h, after cooling to room temperature, the hydrothermal product was washed and suction filtered until the pH was 7.1, and then dried in a vacuum oven at a temperature of 75 ° C to a constant weight to obtain a modified carbon black composite. ;

(3) The dried product of the step (2) is subjected to acid treatment with 2.0 mol/L hydrochloric acid, the liquid-solid ratio of the hydrochloric acid to the dried product is 9, the treatment temperature is 55 ° C, the treatment time is 4 h, and then washed with deionized water. After suction filtration to a neutral pH, the treated product was dried in a vacuum oven at a temperature of 60 ° C for 24 hours to obtain a first dry reactant;

(4) Dissolve 0.6 mg of polyacrylonitrile powder in an appropriate amount of dimethyl sulfoxide, add 100 mL of an aqueous ammonia solution having a concentration of 0.5 mol/L, stir at 70 ° C for 4 min at a rate of 200 rpm, and then slowly add 0.5 mL of positive Ethyl silicate was then heated to 100 ° C in a Teflon vessel, 10 ml of a citric acid solution having a concentration of 0.2 mol/L was added, the temperature was further raised to 150 ° C and stirred at this temperature for 9 h, and the obtained product was subjected to 5000 rpm. The rotation speed is centrifuged, the precipitate is washed with deionized water, and dried at 120 ° C to obtain a second dry reactant;

(5) mixing the first dry reactant obtained in the step (3) and the second dry reactant obtained in the step (4), adding it to distilled water, sonicating at a frequency of 50 kHz for 45 minutes to obtain a mixed dispersion, and adding 0.6 g thereto. Dibutyl sebacate, 0.3g nanometer magnesia, 0.2g antimony trioxide, 0.08g coconut oleic acid monoethanolamide, 0.05g methacryloxypropyltrimethoxysilane, then heated to 110 ° C, heat preservation After stirring for 28 min, after cooling to room temperature, the reaction liquid was filtered to obtain a solid product, which was washed with water and ethanol to neutrality, and then dried in a vacuum oven at 65 ° C for 18 h to obtain a high performance material for a supercapacitor.

Example 3

(1) 15g of iodine value of 105g/Kg of acetylene black was mixed at a liquid-solid ratio of 12 with a sulfuric acid of 92% by mass at 0 °C, and 3 g of sodium p-styrenesulfonate was added at a rate of 10 ° C/min. Heating, heating to 110 ° C, the reaction was held for 3 h, then the reaction mixture was cooled to room temperature, 600 mL of distilled water was added to the reaction mixture for dilution, and then centrifuged at 8000 rpm, the solution was separated and removed, and then 1000 mL of absolute ethanol was used. The lower layer precipitate obtained by centrifugation was washed 3 times, and the washed precipitate was added to distilled water to prepare a liquid-solid ratio mixture of 15 and transferred to a high-pressure hydrothermal reaction vessel to maintain a volume filling ratio of 1.2. After hydrothermal treatment at 350 ° C for 15 h, after cooling to room temperature, the hydrothermal product was washed and suction filtered until the pH was 7.2, and then dried to a constant weight in a vacuum oven at a temperature of 75 ° C to obtain a modified carbon black composite;

(3) The dried product of the step (2) is subjected to acid treatment with 2.0 mol/L hydrochloric acid, and the liquid-solid ratio of the hydrochloric acid to the dried product is 10, the treatment temperature is 55 ° C, the treatment time is 5 h, and then washed with deionized water. Filtered to pH Neutral, the treated product was dried in a vacuum oven at 60 ° C for 24 h to obtain a first dry reactant;

(4) Dissolve 0.6 mg of polyacrylonitrile powder in an appropriate amount of dimethyl sulfoxide, add 100 mL of an aqueous ammonia solution having a concentration of 0.5 mol/L, stir at 70 ° C for 5 min at a rate of 200 rpm, and then slowly add 0.5 mL of positive Ethyl silicate was then heated to 100 ° C in a Teflon vessel, 10 ml of a citric acid solution having a concentration of 0.2 mol/L was added, and the temperature was further raised to 150 ° C and stirred at this temperature for 10 h, and the obtained product was subjected to 5000 rpm. The rotation speed is centrifuged, the precipitate is washed with deionized water, and dried at 120 ° C to obtain a second dry reactant;

(5) mixing the first dry reactant obtained in the step (3) and the second dry reactant obtained in the step (4), adding it to distilled water, sonicating at a frequency of 50 kHz for 45 minutes to obtain a mixed dispersion, and adding 0.6 g thereto. Dibutyl sebacate, 0.3 g of nano-magnesia, 0.2 g of antimony trioxide, 0.08 g of coconut oleic acid monoethanolamide, 0.05 g of 3-glycidoxypropyltrimethoxysilane, and then raised to 110 ° C, The mixture was stirred for 30 minutes, cooled to room temperature, and the reaction liquid was filtered to obtain a solid product, which was washed with water and ethanol to neutrality, and then dried in a vacuum oven at 70 ° C for 18 hours to obtain a high-performance material for a supercapacitor.

Comparative example 1

(4) Dissolve 0.6 mg of polyacrylonitrile powder in an appropriate amount of dimethyl sulfoxide, and then add 100 mL to a concentration of 0.5. A mol/L aqueous ammonia solution was stirred at 70 ° C for 3 min at 70 rpm, then 0.5 mL of tetraethyl orthosilicate was slowly added, and then the temperature was raised to 100 ° C in a Teflon container, and 10 ml of a concentration of 0.2 mol/L was added. The citric acid solution was further heated to 150 ° C and stirred at this temperature for 8 h. The obtained product was centrifuged at 5000 rpm, and the precipitate was washed with deionized water and dried at 120 ° C to obtain a second dry reactant. ;

(5) mixing the first dry reactant obtained in the step (3) and the second dry reactant obtained in the step (4), adding to distilled water, sonicating at a frequency of 50 KHz for 45 minutes to obtain a mixed dispersion, and adding 0.4 g thereto. Dibutyl sebacate, 0.6 g nano-magnesia, 0.5 g antimony trioxide, 0.05 g coconut oil monoethanolamide, 0.05 g vinyl triethoxysilane, then warmed to 110 ° C, stirred for 25 min, cooled to After the reaction mixture was filtered at room temperature to obtain a solid product, it was washed with water and ethanol to neutrality, and then dried in a vacuum oven at 60 ° C for 18 hours to obtain a high performance material for a supercapacitor.

Comparative example 2

(2) mixing the modified carbon black composite obtained in the step (1) with an appropriate amount of distilled water, then adding 0.08 g of nickel chloride, stirring at 3000 rpm for 30 min at room temperature, and transferring the formed mixture to the reaction vessel at 150 The reaction was carried out at ° C for 50 min; after the reaction was completed, the reaction mixture was dried in an oven at 80 ° C overnight to obtain a dried product;

(4) Dissolve 0.6 mg of polyacrylonitrile powder in an appropriate amount of dimethyl sulfoxide, add 100 mL of an aqueous ammonia solution having a concentration of 0.5 mol/L, stir at 70 ° C for 4 min at a rate of 200 rpm, and then slowly add 0.5 mL of positive Ethyl silicate was then heated to 100 ° C in a Teflon vessel, 10 ml of a citric acid solution having a concentration of 0.2 mol/L was added, the temperature was further raised to 150 ° C and stirred at this temperature for 9 h, and the obtained product was subjected to 5000 rpm. Speed into Centrifugal, the precipitate is washed with deionized water, and dried at 120 ° C to obtain a second dry reactant;

Comparative example 3

(1) 15g of iodine value of 105g / Kg of acetylene black was mixed at a liquid-solid ratio of 7 with a sulfuric acid of 92% by mass at 0 ° C, and 3 g of sodium p-styrenesulfonate was added at a rate of 15 ° C / min. Heating, heating to 110 ° C, the reaction was held for 1.5 h, then the reaction mixture was cooled to room temperature, 600 mL of distilled water was added to the reaction mixture for dilution, and then centrifuged at 8000 rpm, the solution was separated and removed, and 1000 mL of water was used. The lower precipitate obtained by centrifugation was washed three times with ethanol, and the washed precipitate was added to distilled water to prepare a liquid-solid ratio mixture of 15 and transferred to a high-pressure hydrothermal reaction vessel to maintain a volume filling ratio of 1.2. After hydrothermal treatment at 350 ° C for 15 h, after cooling to room temperature, the hydrothermal product was washed and suction filtered until the pH was 7.2, and then dried in a vacuum oven at a temperature of 75 ° C to a constant weight to obtain a modified carbon black composite. ;

(2) The modified carbon black composite obtained in the step (1) and 2 g of dilithium hydrogen phosphate were added to distilled water for ultrasonic dispersion at a frequency of 25 KHz for 20 min, then 0.1 g of nickel chloride was added, and stirred at 3000 rpm for 30 min at room temperature. The formed mixture was transferred to a reaction kettle and reacted at 150 ° C for 50 min; after the reaction was completed, the reaction mixture was dried in an oven at 80 ° C overnight to obtain a dried product;

(3) The dried product of the step (2) is subjected to acid treatment with 2.0 mol/L hydrochloric acid, and the liquid-solid ratio of the hydrochloric acid to the dried product is 10, the treatment temperature is 55 ° C, the treatment time is 5 h, and then washed with deionized water. After suction filtration to a neutral pH, the treated product was dried in a vacuum oven at a temperature of 60 ° C for 24 hours to obtain a first dry reactant;

(5) mixing the first dry reactant obtained in the step (3) with the second dry reactant obtained in the step (4), Adding to distilled water, sonicating at a frequency of 50 KHz for 45 min to obtain a mixed dispersion, adding 0.6 g of dibutyl sebacate, 0.3 g of nano-magnesia, 0.2 g of antimony trioxide, 0.08 g of coconut oleic acid monoethanolamide, 0.05 g 3-glycidoxypropyltrimethoxysilane, then warmed to 110 ° C, stirred under heat for 30 min, cooled to room temperature, the reaction solution was filtered to give a solid product, which was washed with water and ethanol to neutral, then placed Drying in a vacuum oven at 70 ° C for 18 h gave a high performance material for supercapacitors.

The high performance materials for the supercapacitors prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to performance tests of specific capacity, capacity retention, energy density, discharge time, and dielectric constant.

Table 1

The high-performance material preparation process for supercapacitor of the invention obtains modified carbon by a series of operations such as heat preservation, cooling, dilution, centrifugation, washing, etc. by heating and heating acetylene black and sulfuric acid and sodium styrene sulfonate. The black composite is further reacted with lithium dihydrogen phosphate and nickel chloride in a reaction vessel, dried, and then subjected to an acid treatment, and then reacted with acrylonitrile powder, dimethyl sulfoxide, orthosilicate, etc. at a high temperature. The reactants are mixed, ultrasonically dispersed by adding distilled water, and dibutyl sebacate, nano-magnesia oxide, antimony trioxide, coconut oleic acid monoethanolamide, silane coupling agent are added for high-temperature reaction, and finally, the product is obtained by washing and vacuum drying. . The high-performance materials prepared for supercapacitors have better specific capacity, good cycle stability, high energy density and good electrical conductivity, and have good application prospects. The high-performance material raw material for super capacitor of the invention is cheap, simple in process, suitable for large-scale industrial application, and has strong practicability.

The above is only the embodiment of the present invention, and is not intended to limit the scope of the invention, and the equivalent structure or equivalent process transformation made by using the content of the specification of the present invention, or directly or indirectly applied in other related technical fields, The same is included in the scope of patent protection of the present invention.

Claims

A method for preparing a high performance material for a supercapacitor, comprising the steps of:

(1) 15g of acetylene black is mixed at a liquid-solid ratio of 8-12 with a sulfuric acid having a mass concentration of 92% at 0 ° C, and 3 g of sodium p-styrene sulfonate is added thereto, and heated at a rate of 8-10 ° C / min to raise the temperature. After the temperature is maintained at 110 ° C for 2-3 h, the reaction mixture is cooled to room temperature, 600 mL of distilled water is added to the reaction mixture for dilution, and then centrifuged at 7000-8000 rpm to separate the solution and then use 1000 mL of anhydrous. The lower precipitate obtained by centrifugation is washed 2-3 times with ethanol, and the washed precipitate is added to distilled water to prepare a liquid mixture having a liquid-solid ratio of 15 and transferred to a high-pressure hydrothermal reaction vessel to maintain a volume filling ratio thereof. 1.2, hydrothermal treatment at 350 ° C for 10-15h, after cooling to room temperature, the hydrothermal product is washed and suction filtered until the pH is 7.0-7.2, and then dried in a vacuum oven at a temperature of 75 ° C to a constant weight, Modified carbon black composite;

(2) The modified carbon black composite obtained in the step (1) and 2 g of dilithium hydrogen phosphate were added to distilled water for ultrasonic dispersion at a frequency of 25 KHz for 30 min, then 0.08 g of nickel chloride was added, and stirred at 3000 rpm for 30 min at room temperature. The formed mixture was transferred to a reaction kettle and reacted at 150 ° C for 50 min; after the reaction was completed, the reaction mixture was dried in an oven at 80 ° C overnight to obtain a dried product;

(3) The dried product of the step (2) is subjected to acid treatment with 2.0 mol/L hydrochloric acid, and the liquid-solid ratio of the hydrochloric acid to the dried product is 8-10, the treatment temperature is 55 ° C, and the treatment time is 3-5 h, followed by Deionized water washing and suction filtration until the pH is neutral, and the treated product is dried in a vacuum drying oven at a temperature of 60 ° C for 24 hours to obtain a first dry reactant;

(4) Dissolve 0.6 mg of polyacrylonitrile powder in an appropriate amount of dimethyl sulfoxide, add 100 mL of an aqueous ammonia solution having a concentration of 0.5 mol/L, stir at 70 ° C for 3-5 min at a rate of 200 rpm, and then slowly add 0.5. mL of tetraethyl orthosilicate, then warmed to 100 ° C in a Teflon container, add 10 ml of citric acid solution with a concentration of 0.2 mol / L, continue to raise the temperature to 150 ° C and stir at this temperature for 8-10 h, will get The product was centrifuged at 5000 rpm, and the precipitate was washed with deionized water and dried at 120 ° C to obtain a second dried reactant;

(5) mixing the first dry reactant obtained in the step (3) and the second dry reactant obtained in the step (4), adding to distilled water, sonicating at a frequency of 50 KHz for 45 minutes to obtain a mixed dispersion, and adding 0.5- 0.8 g of dibutyl sebacate, 0.2-0.4 g of nano-magnesia, 0.1-0.3 g of antimony trioxide, 0.06-0.1 g of coconut oleic acid monoethanolamide, 0.05-0.08 g of silane coupling agent, and then raised to 110 ° C The mixture was stirred for 25-30 min. After cooling to room temperature, the reaction solution was filtered to obtain a solid product, which was washed with water and ethanol to neutrality, and then dried in a vacuum oven at 60-70 ° C for 18 h to obtain a high for a supercapacitor. Performance material.
The method for preparing a high performance material for a supercapacitor according to claim 1, wherein the iodine carbon black in the step (1) has an iodine absorption value of 105 g/kg.
The method for preparing a high performance material for a supercapacitor according to claim 1, wherein in the step (5), 0.6 g of dibutyl sebacate and 0.3 g of nanometer magnesium oxide are added to the mixed dispersion. 0.2 g of antimony trioxide, 0.08 g of coconut oleic acid monoethanolamide, 0.05 g of a silane coupling agent.
The method for preparing a high performance material for a supercapacitor according to claim 1, wherein the silane coupling agent in the step (5) is selected from the group consisting of vinyl triethoxysilane and methacryloyloxy Any one of propyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane.
Use of a high performance material for a supercapacitor obtained by the preparation process according to any one of claims 1 to 4 in the preparation of a supercapacitor.