WO2018184341A1 - 一种用于超级电容器的高性能材料的制备方法 - Google Patents

一种用于超级电容器的高性能材料的制备方法 Download PDF

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WO2018184341A1
WO2018184341A1 PCT/CN2017/098517 CN2017098517W WO2018184341A1 WO 2018184341 A1 WO2018184341 A1 WO 2018184341A1 CN 2017098517 W CN2017098517 W CN 2017098517W WO 2018184341 A1 WO2018184341 A1 WO 2018184341A1
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dried
supercapacitor
added
temperature
product
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PCT/CN2017/098517
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French (fr)
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黄啸谷
张其土
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苏州海凌达电子科技有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • the use of high performance materials for supercapacitors prepared by the preparation process in the preparation of supercapacitors is also disclosed.
  • a method for preparing a high performance material for a supercapacitor comprising the steps of:
  • 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.
  • 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;
  • 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;
  • 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 iodine carbon black of the step (1) has an iodine absorption value of 105 g/Kg.
  • 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.
  • 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.
  • the invention has the following beneficial effects:
  • 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.
  • 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.
  • 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.
  • 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;
  • 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;
  • 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.
  • 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. ;
  • 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;
  • 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.
  • 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;
  • step (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;
  • 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.
  • 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.
  • 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;
  • 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;
  • 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.
  • 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. ;
  • 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;
  • 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.
  • 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. ;
  • 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;
  • 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.
  • 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.

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Abstract

本发明公开了一种用于超级电容器的高性能材料的制备方法，该工艺通过将乙炔炭黑和硫酸、苯乙烯磺酸钠进行混合加热，经保温、冷却等一系列操作后得到改性炭黑复合物，再加入磷酸氢二锂、氯化镍于反应釜中进行反应，酸处理后将其与丙烯腈粉末等成分经高温反应的反应物混合，加入蒸馏水超声分散，并添加癸二酸二丁酯、纳米氧化镁、三氧化铋、椰子油酸单乙醇酰胺、硅烷偶联剂进行高温反应，最后通过洗涤、真空干燥得到成品。制备而成的用于超级电容器的高性能材料，其比容量大、循环稳定性好、能量密度高、导电性能佳，具有较好的应用前景。同时还公开了由该制备工艺制得的用于超级电容器的高性能材料在制备超级电容器中的应用。

Description

一种用于超级电容器的高性能材料的制备方法 技术领域
本发明涉及电容器材料这一技术领域，特别涉及到一种用于超级电容器的高性能材料的制备方法。
背景技术
超级电容器是介于传统电容器和电池之间的储能器件，广泛应用于备用电源、便携式移动电源、混合动力汽车电源等领域，具有良好的应用前景。其既具有电容器高功率和可以快速充放电的特点，又具有电化学电池的能量存储特性。从整体结构上看，超级电容器主要由正负电极、电解液、隔膜、引线和封装材料组成。超级电容器按照储能机理分为双电层电容器和法拉第准电容器，双电层电容器的能量存储与转换是基于双电层理论，利用电极/电解液界面电荷分离形成双电层来实现能量存储的一种新型储能器件。超级电容器的性能主要取决于正负电极片上的电极材料。根据储存和转化电能机理的不同，超级电容器主要分为赝电容超级电容器和双电层超级电容器。赝电容超级电容器是通过电化学活性物质在电极表面和电解液之间发生法拉第氧化还原反应来进行能量的存储和转化，所用电极材料主要以比电容较大的金属氧化物和导电聚合物为主，因而赝电容超级电容器具有较高的能量密度，但电极材料导电性较差，造成超级电容器的倍率性能和循环稳定性较差。双电层超级电容器通过在电极上富集离子来储存电荷，电极主要采用比表面积大的活性炭、碳纳米管、碳气凝胶、石墨烯等碳材料，超级电容器的倍率性能和循环性能较好。但是，双电层超级电容器采用的电极活性材料一般其比电容值相对较低，且导电性较差，导致超级电容器的能量密度偏低，限制了其发展。
发明内容
为解决上述技术问题，本发明提供一种用于超级电容器的高性能材料的制备方法，该工艺通过将乙炔炭黑和硫酸、苯乙烯磺酸钠进行混合加热，经保温、冷却、稀释、离心分离、洗涤等一系列操作后得到改性炭黑复合物，再加入磷酸氢二锂、氯化镍于反应釜中进行反应，干燥后进行酸处理，再将其与丙烯腈粉末、二甲基亚砜、正硅酸乙酯等经高温反应的反应物混合，加入蒸馏水超声分散，并添加癸二酸二丁酯、纳米氧化镁、三氧化铋、椰子油酸单乙醇酰胺、硅烷偶联剂进行高温反应，最后通过洗涤、真空干燥得到成品。制备而成的用于超级电容器的高性能材料，其比容量大、循环稳定性好、能量密度高、导电性能佳，具有较好的应用前景。同时还公开了由该制备工艺制得的用于超级电容器的高性能材料在制备超级电容器中的应用。
本发明的目的可以通过以下技术方案实现：
一种用于超级电容器的高性能材料的制备方法，包括以下步骤：
(1)将15g乙炔炭黑在0℃条件下按液固比8-12与质量浓度92％的硫酸混合，加入3g对苯乙烯磺酸钠，以8-10℃/min的速率加热，升温至110℃后保温反应持2-3h，随后将反应混合液冷却至室温，向反应混合液中加入600mL蒸馏水进行稀释，然后按照7000-8000rpm的转速进行离心，分离去除溶液，再用1000mL无水乙醇将离心分离得到的下层沉淀物洗涤2-3次，将洗涤后的沉淀物加入蒸馏水配成液固比为15的混合液并将转移到高压水热反应釜中，保持其体积填充率为1.2，在350℃下水热处理10-15h，冷却至室温后将水热产物洗涤、抽滤，直至pH值为7.0-7.2，然后放入温度为75℃的真空干燥箱中干燥至恒重，得到改性碳黑复合物；
(2)将步骤(1)得到的改性炭黑复合物与2g磷酸氢二锂加入到蒸馏水中以25KHz的频率超声分散30min，然后加入氯化镍0.08g，在室温下以3000rpm搅拌30min，将形成的混合液转移到反应釜中，在150℃下反应50min；反应结束后，将反应混合液置于80℃烘箱中干燥过夜，得到干燥产物；
(3)用2.0mol/L的盐酸对步骤(2)的干燥产物进行酸处理，盐酸与干燥产物的液固比为8-10、处理温度为55℃、处理时间为3-5h，随后用去离子水洗涤抽滤至pH值为中性，将处理后的产物放入温度为60℃的真空干燥箱中干燥24h，得第一干燥反应物；
(4)将0.6mg聚丙烯腈粉末溶解于适量的二甲基亚砜，再加入100mL浓度为0.5mol/L的氨水溶液，以200rpm的速率在70℃下搅拌3-5min，然后缓慢加入0.5mL正硅酸乙酯，然后在聚四氟乙烯容器中升温至100℃，加入10ml浓度为0.2mol/L的柠檬酸溶液，继续升温至150℃并在此温度下搅拌8-10h，将得到的产物按照5000rpm的转速进行离心，沉淀物用去离子水进行洗涤，在120℃下干燥后得到第二干燥反应物；
(5)将步骤(3)得到的第一干燥反应物和步骤(4)得到的第二干燥反应物混合，加入蒸馏水中，以50KHz的频率超声处理45min得到混合分散液，向其中添加0.5-0.8g癸二酸二丁酯，0.2-0.4g纳米氧化镁，0.1-0.3g三氧化铋，0.06-0.1g椰子油酸单乙醇酰胺，0.05-0.08g硅烷偶联剂，然后升温至110℃，保温搅拌25-30min，冷却至室温后将反应液过滤得到固态产物，用水和乙醇将其洗涤至中性，再置于60-70℃真空干燥箱中干燥18h，得到用于超级电容器的高性能材料。
优选地，所述步骤(1)中乙炔炭黑的吸碘值为105g/Kg。
优选地，所述步骤(5)中向混合分散液中添加0.6g癸二酸二丁酯，0.3g纳米氧化镁，0.2g三氧化铋，0.08g椰子油酸单乙醇酰胺，0.05g硅烷偶联剂。
优选地，所述步骤(5)中的硅烷偶联剂选自乙烯基三乙氧基硅烷、甲基丙烯酰氧基丙基三甲氧基硅烷、3-缩水甘油醚氧基丙基三甲氧基硅烷中的任意一种。
本发明还提供了由上述制备工艺得到的用于超级电容器的高性能材料在制备超级电容器中的应用。
本发明与现有技术相比，其有益效果为：
(1)本发明的用于超级电容器的高性能材料制备工艺通过将乙炔炭黑和硫酸、苯乙烯磺酸钠进行混合加热，经保温、冷却、稀释、离心分离、洗涤等一系列操作后得到改性炭黑复合物，再加入磷酸氢二锂、氯化镍于反应釜中进行反应，干燥后进行酸处理，再将其与丙烯腈粉末、二甲基亚砜、正硅酸乙酯等经高温反应的反应物混合，加入蒸馏水超声分散，并添加癸二酸二丁酯、纳米氧化镁、三氧化铋、椰子油酸单乙醇酰胺、硅烷偶联剂进行高温反应，最后通过洗涤、真空干燥得到成品。制备而成的用于超级电容器的高性能材料，其比容量大、循环稳定性好、能量密度高、导电性能佳，具有较好的应用前景。
(2)本发明的用于超级电容器的高性能材料原料廉价、工艺简单，适于大规模工业化运用，实用性强。
具体实施方式
下面结合具体实施例对发明的技术方案进行详细说明。
实施例1
(1)将15g吸碘值为105g/Kg乙炔炭黑在0℃条件下按液固比8与质量浓度92％的硫酸混合，加入3g对苯乙烯磺酸钠，以8℃/min的速率加热，升温至110℃后保温反应持2h，随后将反应混合液冷却至室温，向反应混合液中加入600mL蒸馏水进行稀释，然后按照7000rpm的转速进行离心，分离去除溶液，再用1000mL无水乙醇将离心分离得到的下层沉淀物洗涤2次，将洗涤后的沉淀物加入蒸馏水配成液固比为15的混合液并将转移到高压水热反应釜中，保持其体积填充率为1.2，在350℃下水热处理10h，冷却至室温后将水热产物洗涤、抽滤，直至pH值为7.0，然后放入温度为75℃的真空干燥箱中干燥至恒重，得到改性碳黑复合物；
(2)将步骤(1)得到的改性炭黑复合物与2g磷酸氢二锂加入到蒸馏水中以25KHz的频率超声分散30min，然后加入氯化镍0.08g，在室温下以3000rpm搅拌30min，将 形成的混合液转移到反应釜中，在150℃下反应50min；反应结束后，将反应混合液置于80℃烘箱中干燥过夜，得到干燥产物；
(3)用2.0mol/L的盐酸对步骤(2)的干燥产物进行酸处理，盐酸与干燥产物的液固比为8、处理温度为55℃、处理时间为3h，随后用去离子水洗涤抽滤至pH值为中性，将处理后的产物放入温度为60℃的真空干燥箱中干燥24h，得第一干燥反应物；
(4)将0.6mg聚丙烯腈粉末溶解于适量的二甲基亚砜，再加入100mL浓度为0.5mol/L的氨水溶液，以200rpm的速率在70℃下搅拌3min，然后缓慢加入0.5mL正硅酸乙酯，然后在聚四氟乙烯容器中升温至100℃，加入10ml浓度为0.2mol/L的柠檬酸溶液，继续升温至150℃并在此温度下搅拌8h，将得到的产物按照5000rpm的转速进行离心，沉淀物用去离子水进行洗涤，在120℃下干燥后得到第二干燥反应物；
(5)将步骤(3)得到的第一干燥反应物和步骤(4)得到的第二干燥反应物混合，加入蒸馏水中，以50KHz的频率超声处理45min得到混合分散液，向其中添加0.6g癸二酸二丁酯，0.3g纳米氧化镁，0.2g三氧化铋，0.08g椰子油酸单乙醇酰胺，0.05g乙烯基三乙氧基硅烷，然后升温至110℃，保温搅拌25min，冷却至室温后将反应液过滤得到固态产物，用水和乙醇将其洗涤至中性，再置于60℃真空干燥箱中干燥18h，得到用于超级电容器的高性能材料。
制得的用于超级电容器的高性能材料的性能测试结果如表1所示。
实施例2
(1)将15g吸碘值为105g/Kg乙炔炭黑在0℃条件下按液固比10与质量浓度92％的硫酸混合，加入3g对苯乙烯磺酸钠，以9℃/min的速率加热，升温至110℃后保温反应持2.5h，随后将反应混合液冷却至室温，向反应混合液中加入600mL蒸馏水进行稀释，然后按照7500rpm的转速进行离心，分离去除溶液，再用1000mL无水乙醇将离心分离得到的下层沉淀物洗涤2次，将洗涤后的沉淀物加入蒸馏水配成液固比为15的混合液并将转移到高压水热反应釜中，保持其体积填充率为1.2，在350℃下水热处理12h，冷却至室温后将水热产物洗涤、抽滤，直至pH值为7.1，然后放入温度为75℃的真空干燥箱中干燥至恒重，得到改性碳黑复合物；
(2)将步骤(1)得到的改性炭黑复合物与2g磷酸氢二锂加入到蒸馏水中以25KHz的频率超声分散30min，然后加入氯化镍0.08g，在室温下以3000rpm搅拌30min，将形成的混合液转移到反应釜中，在150℃下反应50min；反应结束后，将反应混合液置于80℃烘箱中干燥过夜，得到干燥产物；
(3)用2.0mol/L的盐酸对步骤(2)的干燥产物进行酸处理，盐酸与干燥产物的液固比为9、处理温度为55℃、处理时间为4h，随后用去离子水洗涤抽滤至pH值为中性，将处理后的产物放入温度为60℃的真空干燥箱中干燥24h，得第一干燥反应物；
(4)将0.6mg聚丙烯腈粉末溶解于适量的二甲基亚砜，再加入100mL浓度为0.5mol/L的氨水溶液，以200rpm的速率在70℃下搅拌4min，然后缓慢加入0.5mL正硅酸乙酯，然后在聚四氟乙烯容器中升温至100℃，加入10ml浓度为0.2mol/L的柠檬酸溶液，继续升温至150℃并在此温度下搅拌9h，将得到的产物按照5000rpm的转速进行离心，沉淀物用去离子水进行洗涤，在120℃下干燥后得到第二干燥反应物；
(5)将步骤(3)得到的第一干燥反应物和步骤(4)得到的第二干燥反应物混合，加入蒸馏水中，以50KHz的频率超声处理45min得到混合分散液，向其中添加0.6g癸二酸二丁酯，0.3g纳米氧化镁，0.2g三氧化铋，0.08g椰子油酸单乙醇酰胺，0.05g甲基丙烯酰氧基丙基三甲氧基硅烷，然后升温至110℃，保温搅拌28min，冷却至室温后将反应液过滤得到固态产物，用水和乙醇将其洗涤至中性，再置于65℃真空干燥箱中干燥18h，得到用于超级电容器的高性能材料。
制得的用于超级电容器的高性能材料的性能测试结果如表1所示。
实施例3
(1)将15g吸碘值为105g/Kg乙炔炭黑在0℃条件下按液固比12与质量浓度92％的硫酸混合，加入3g对苯乙烯磺酸钠，以10℃/min的速率加热，升温至110℃后保温反应持3h，随后将反应混合液冷却至室温，向反应混合液中加入600mL蒸馏水进行稀释，然后按照8000rpm的转速进行离心，分离去除溶液，再用1000mL无水乙醇将离心分离得到的下层沉淀物洗涤3次，将洗涤后的沉淀物加入蒸馏水配成液固比为15的混合液并将转移到高压水热反应釜中，保持其体积填充率为1.2，在350℃下水热处理15h，冷却至室温后将水热产物洗涤、抽滤，直至pH值为7.2，然后放入温度为75℃的真空干燥箱中干燥至恒重，得到改性碳黑复合物；
(2)将步骤(1)得到的改性炭黑复合物与2g磷酸氢二锂加入到蒸馏水中以25KHz的频率超声分散30min，然后加入氯化镍0.08g，在室温下以3000rpm搅拌30min，将形成的混合液转移到反应釜中，在150℃下反应50min；反应结束后，将反应混合液置于80℃烘箱中干燥过夜，得到干燥产物；
(3)用2.0mol/L的盐酸对步骤(2)的干燥产物进行酸处理，盐酸与干燥产物的液固比为10、处理温度为55℃、处理时间为5h，随后用去离子水洗涤抽滤至pH值为 中性，将处理后的产物放入温度为60℃的真空干燥箱中干燥24h，得第一干燥反应物；
(4)将0.6mg聚丙烯腈粉末溶解于适量的二甲基亚砜，再加入100mL浓度为0.5mol/L的氨水溶液，以200rpm的速率在70℃下搅拌5min，然后缓慢加入0.5mL正硅酸乙酯，然后在聚四氟乙烯容器中升温至100℃，加入10ml浓度为0.2mol/L的柠檬酸溶液，继续升温至150℃并在此温度下搅拌10h，将得到的产物按照5000rpm的转速进行离心，沉淀物用去离子水进行洗涤，在120℃下干燥后得到第二干燥反应物；
(5)将步骤(3)得到的第一干燥反应物和步骤(4)得到的第二干燥反应物混合，加入蒸馏水中，以50KHz的频率超声处理45min得到混合分散液，向其中添加0.6g癸二酸二丁酯，0.3g纳米氧化镁，0.2g三氧化铋，0.08g椰子油酸单乙醇酰胺，0.05g 3-缩水甘油醚氧基丙基三甲氧基硅烷，然后升温至110℃，保温搅拌30min，冷却至室温后将反应液过滤得到固态产物，用水和乙醇将其洗涤至中性，再置于70℃真空干燥箱中干燥18h，得到用于超级电容器的高性能材料。
制得的用于超级电容器的高性能材料的性能测试结果如表1所示。
对比例1
(1)将15g吸碘值为105g/Kg乙炔炭黑在0℃条件下按液固比8与质量浓度92％的硫酸混合，加入3g对苯乙烯磺酸钠，以8℃/min的速率加热，升温至110℃后保温反应持2h，随后将反应混合液冷却至室温，向反应混合液中加入600mL蒸馏水进行稀释，然后按照7000rpm的转速进行离心，分离去除溶液，再用1000mL无水乙醇将离心分离得到的下层沉淀物洗涤2次，将洗涤后的沉淀物加入蒸馏水配成液固比为15的混合液并将转移到高压水热反应釜中，保持其体积填充率为1.2，在350℃下水热处理10h，冷却至室温后将水热产物洗涤、抽滤，直至pH值为7.0，然后放入温度为75℃的真空干燥箱中干燥至恒重，得到改性碳黑复合物；
(2)将步骤(1)得到的改性炭黑复合物与2g磷酸氢二锂加入到蒸馏水中以25KHz的频率超声分散30min，然后加入氯化镍0.08g，在室温下以3000rpm搅拌30min，将形成的混合液转移到反应釜中，在150℃下反应50min；反应结束后，将反应混合液置于80℃烘箱中干燥过夜，得到干燥产物；
(3)用2.0mol/L的盐酸对步骤(2)的干燥产物进行酸处理，盐酸与干燥产物的液固比为8、处理温度为55℃、处理时间为3h，随后用去离子水洗涤抽滤至pH值为中性，将处理后的产物放入温度为60℃的真空干燥箱中干燥24h，得第一干燥反应物；
(4)将0.6mg聚丙烯腈粉末溶解于适量的二甲基亚砜，再加入100mL浓度为0.5 mol/L的氨水溶液，以200rpm的速率在70℃下搅拌3min，然后缓慢加入0.5mL正硅酸乙酯，然后在聚四氟乙烯容器中升温至100℃，加入10ml浓度为0.2mol/L的柠檬酸溶液，继续升温至150℃并在此温度下搅拌8h，将得到的产物按照5000rpm的转速进行离心，沉淀物用去离子水进行洗涤，在120℃下干燥后得到第二干燥反应物；
(5)将步骤(3)得到的第一干燥反应物和步骤(4)得到的第二干燥反应物混合，加入蒸馏水中，以50KHz的频率超声处理45min得到混合分散液，向其中添加0.4g癸二酸二丁酯，0.6g纳米氧化镁，0.5g三氧化铋，0.05g椰子油酸单乙醇酰胺，0.05g乙烯基三乙氧基硅烷，然后升温至110℃，保温搅拌25min，冷却至室温后将反应液过滤得到固态产物，用水和乙醇将其洗涤至中性，再置于60℃真空干燥箱中干燥18h，得到用于超级电容器的高性能材料。
制得的用于超级电容器的高性能材料的性能测试结果如表1所示。
对比例2
(1)将15g吸碘值为105g/Kg乙炔炭黑在0℃条件下按液固比10与质量浓度92％的硫酸混合，加入3g对苯乙烯磺酸钠，以9℃/min的速率加热，升温至110℃后保温反应持2.5h，随后将反应混合液冷却至室温，向反应混合液中加入600mL蒸馏水进行稀释，然后按照7500rpm的转速进行离心，分离去除溶液，再用1000mL无水乙醇将离心分离得到的下层沉淀物洗涤2次，将洗涤后的沉淀物加入蒸馏水配成液固比为15的混合液并将转移到高压水热反应釜中，保持其体积填充率为1.2，在350℃下水热处理12h，冷却至室温后将水热产物洗涤、抽滤，直至pH值为7.1，然后放入温度为75℃的真空干燥箱中干燥至恒重，得到改性碳黑复合物；
(2)将步骤(1)得到的改性炭黑复合物与适量蒸馏水混合，然后加入氯化镍0.08g，在室温下以3000rpm搅拌30min，将形成的混合液转移到反应釜中，在150℃下反应50min；反应结束后，将反应混合液置于80℃烘箱中干燥过夜，得到干燥产物；
(3)用2.0mol/L的盐酸对步骤(2)的干燥产物进行酸处理，盐酸与干燥产物的液固比为9、处理温度为55℃、处理时间为4h，随后用去离子水洗涤抽滤至pH值为中性，将处理后的产物放入温度为60℃的真空干燥箱中干燥24h，得第一干燥反应物；
(4)将0.6mg聚丙烯腈粉末溶解于适量的二甲基亚砜，再加入100mL浓度为0.5mol/L的氨水溶液，以200rpm的速率在70℃下搅拌4min，然后缓慢加入0.5mL正硅酸乙酯，然后在聚四氟乙烯容器中升温至100℃，加入10ml浓度为0.2mol/L的柠檬酸溶液，继续升温至150℃并在此温度下搅拌9h，将得到的产物按照5000rpm的转速进 行离心，沉淀物用去离子水进行洗涤，在120℃下干燥后得到第二干燥反应物；
(5)将步骤(3)得到的第一干燥反应物和步骤(4)得到的第二干燥反应物混合，加入蒸馏水中，以50KHz的频率超声处理45min得到混合分散液，向其中添加0.6g癸二酸二丁酯，0.3g纳米氧化镁，0.2g三氧化铋，0.08g椰子油酸单乙醇酰胺，0.05g甲基丙烯酰氧基丙基三甲氧基硅烷，然后升温至110℃，保温搅拌28min，冷却至室温后将反应液过滤得到固态产物，用水和乙醇将其洗涤至中性，再置于65℃真空干燥箱中干燥18h，得到用于超级电容器的高性能材料。
制得的用于超级电容器的高性能材料的性能测试结果如表1所示。
对比例3
(1)将15g吸碘值为105g/Kg乙炔炭黑在0℃条件下按液固比7与质量浓度92％的硫酸混合，加入3g对苯乙烯磺酸钠，以15℃/min的速率加热，升温至110℃后保温反应持1.5h，随后将反应混合液冷却至室温，向反应混合液中加入600mL蒸馏水进行稀释，然后按照8000rpm的转速进行离心，分离去除溶液，再用1000mL无水乙醇将离心分离得到的下层沉淀物洗涤3次，将洗涤后的沉淀物加入蒸馏水配成液固比为15的混合液并将转移到高压水热反应釜中，保持其体积填充率为1.2，在350℃下水热处理15h，冷却至室温后将水热产物洗涤、抽滤，直至pH值为7.2，然后放入温度为75℃的真空干燥箱中干燥至恒重，得到改性碳黑复合物；
(2)将步骤(1)得到的改性炭黑复合物与2g磷酸氢二锂加入到蒸馏水中以25KHz的频率超声分散20min，然后加入氯化镍0.1g，在室温下以3000rpm搅拌30min，将形成的混合液转移到反应釜中，在150℃下反应50min；反应结束后，将反应混合液置于80℃烘箱中干燥过夜，得到干燥产物；
(3)用2.0mol/L的盐酸对步骤(2)的干燥产物进行酸处理，盐酸与干燥产物的液固比为10、处理温度为55℃、处理时间为5h，随后用去离子水洗涤抽滤至pH值为中性，将处理后的产物放入温度为60℃的真空干燥箱中干燥24h，得第一干燥反应物；
(4)将0.6mg聚丙烯腈粉末溶解于适量的二甲基亚砜，再加入100mL浓度为0.5mol/L的氨水溶液，以200rpm的速率在70℃下搅拌5min，然后缓慢加入0.5mL正硅酸乙酯，然后在聚四氟乙烯容器中升温至100℃，加入10ml浓度为0.2mol/L的柠檬酸溶液，继续升温至150℃并在此温度下搅拌10h，将得到的产物按照5000rpm的转速进行离心，沉淀物用去离子水进行洗涤，在120℃下干燥后得到第二干燥反应物；
(5)将步骤(3)得到的第一干燥反应物和步骤(4)得到的第二干燥反应物混合， 加入蒸馏水中，以50KHz的频率超声处理45min得到混合分散液，向其中添加0.6g癸二酸二丁酯，0.3g纳米氧化镁，0.2g三氧化铋，0.08g椰子油酸单乙醇酰胺，0.05g 3-缩水甘油醚氧基丙基三甲氧基硅烷，然后升温至110℃，保温搅拌30min，冷却至室温后将反应液过滤得到固态产物，用水和乙醇将其洗涤至中性，再置于70℃真空干燥箱中干燥18h，得到用于超级电容器的高性能材料。
制得的用于超级电容器的高性能材料的性能测试结果如表1所示。
将实施例1-3和对比例1-3的制得的用于超级电容器的高性能材料进行比容量、容量保留率、能量密度、放电时间和介电常数这几项性能测试。
表1
Figure PCTCN2017098517-appb-000001
本发明的用于超级电容器的高性能材料制备工艺通过将乙炔炭黑和硫酸、苯乙烯磺酸钠进行混合加热，经保温、冷却、稀释、离心分离、洗涤等一系列操作后得到改性炭黑复合物，再加入磷酸氢二锂、氯化镍于反应釜中进行反应，干燥后进行酸处理，再将其与丙烯腈粉末、二甲基亚砜、正硅酸乙酯等经高温反应的反应物混合，加入蒸馏水超声分散，并添加癸二酸二丁酯、纳米氧化镁、三氧化铋、椰子油酸单乙醇酰胺、硅烷偶联剂进行高温反应，最后通过洗涤、真空干燥得到成品。制备而成的用于超级电容器的高性能材料，其比容量大、循环稳定性好、能量密度高、导电性能佳，具有较好的应用前景。本发明的用于超级电容器的高性能材料原料廉价、工艺简单，适于大规模工业化运用，实用性强。
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。

Claims (5)

  1. 一种用于超级电容器的高性能材料的制备方法，其特征在于，包括以下步骤：
    (1)将15g乙炔炭黑在0℃条件下按液固比8-12与质量浓度92％的硫酸混合，加入3g对苯乙烯磺酸钠，以8-10℃/min的速率加热，升温至110℃后保温反应持2-3h，随后将反应混合液冷却至室温，向反应混合液中加入600mL蒸馏水进行稀释，然后按照7000-8000rpm的转速进行离心，分离去除溶液，再用1000mL无水乙醇将离心分离得到的下层沉淀物洗涤2-3次，将洗涤后的沉淀物加入蒸馏水配成液固比为15的混合液并将转移到高压水热反应釜中，保持其体积填充率为1.2，在350℃下水热处理10-15h，冷却至室温后将水热产物洗涤、抽滤，直至pH值为7.0-7.2，然后放入温度为75℃的真空干燥箱中干燥至恒重，得到改性碳黑复合物；
    (2)将步骤(1)得到的改性炭黑复合物与2g磷酸氢二锂加入到蒸馏水中以25KHz的频率超声分散30min，然后加入氯化镍0.08g，在室温下以3000rpm搅拌30min，将形成的混合液转移到反应釜中，在150℃下反应50min；反应结束后，将反应混合液置于80℃烘箱中干燥过夜，得到干燥产物；
    (3)用2.0mol/L的盐酸对步骤(2)的干燥产物进行酸处理，盐酸与干燥产物的液固比为8-10、处理温度为55℃、处理时间为3-5h，随后用去离子水洗涤抽滤至pH值为中性，将处理后的产物放入温度为60℃的真空干燥箱中干燥24h，得第一干燥反应物；
    (4)将0.6mg聚丙烯腈粉末溶解于适量的二甲基亚砜，再加入100mL浓度为0.5mol/L的氨水溶液，以200rpm的速率在70℃下搅拌3-5min，然后缓慢加入0.5mL正硅酸乙酯，然后在聚四氟乙烯容器中升温至100℃，加入10ml浓度为0.2mol/L的柠檬酸溶液，继续升温至150℃并在此温度下搅拌8-10h，将得到的产物按照5000rpm的转速进行离心，沉淀物用去离子水进行洗涤，在120℃下干燥后得到第二干燥反应物；
    (5)将步骤(3)得到的第一干燥反应物和步骤(4)得到的第二干燥反应物混合，加入蒸馏水中，以50KHz的频率超声处理45min得到混合分散液，向其中添加0.5-0.8g癸二酸二丁酯，0.2-0.4g纳米氧化镁，0.1-0.3g三氧化铋，0.06-0.1g椰子油酸单乙醇酰胺，0.05-0.08g硅烷偶联剂，然后升温至110℃，保温搅拌25-30min，冷却至室温后将反应液过滤得到固态产物，用水和乙醇将其洗涤至中性，再置于60-70℃真空干燥箱中干燥18h，得到用于超级电容器的高性能材料。
  2. 根据权利要求1所述的用于超级电容器的高性能材料的制备方法，其特征在于，所述步骤(1)中乙炔炭黑的吸碘值为105g/Kg。
  3. 根据权利要求1所述的用于超级电容器的高性能材料的制备方法，其特征在于，所述步骤(5)中向混合分散液中添加0.6g癸二酸二丁酯，0.3g纳米氧化镁，0.2g三氧化铋，0.08g椰子油酸单乙醇酰胺，0.05g硅烷偶联剂。
  4. 根据权利要求1所述的用于超级电容器的高性能材料的制备方法，其特征在于，所述步骤(5)中的硅烷偶联剂选自乙烯基三乙氧基硅烷、甲基丙烯酰氧基丙基三甲氧基硅烷、3-缩水甘油醚氧基丙基三甲氧基硅烷中的任意一种。
  5. 根据权利要求1-4任一项所述制备工艺得到的用于超级电容器的高性能材料在制备超级电容器中的应用。
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