互穿网络结构导电高分子复合固态电解质的研制与应用
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摘要
采用聚四氟乙烯(PTEF)溶液对已形成钽氧化膜(Ta2O5)的Ta多孔体阳极表面进行预处理,在钽阳极微孔内形成具有许多通孔的非导电性高分子互穿网络结构,然后采用化学氧化聚合法,在互穿网络结构的通孔中原位聚合聚3,4-亚乙基二氧噻吩(PEDT)导电高分子聚合物,从而在Ta阳极体表面形成导电性高分子复合柔性固态电解质层。实验结果表明,采用20%体积浓度的PTEF水性分散液,原位聚合PEDT可以在钽阳极表面形成高机械强度的复合固态电解质层,用其制作的钽电解电容器,平均漏电流<15μA,产品的平均等效串联电阻(ESR)值<50mΩ。
Polytetrafluoroethylene(PTEF)solution was used to pretreat the anodic surface of a Ta porous body formed by a tantalum oxide film(Ta2 O5),and non-conductive polymer interpenetrating network with many through holes was formed in the micro porous of tantalum anode.Then the chemical polymerization method was used to polymerize 3,4-ethylene glycol two oxygen thiophene(PEDT)in the interpenetrating network hole,so a conductive polymer composite flexible solid electrolyte layer is formed on the surface of Ta anode.The experimental results show that use 20% volume of PTEF water dispersions,a composite solid electrolyte layer with high mechanical strength would be coated on the surface of the tantalum anode,The average leakage current of the tantalum electrolytic capacitor is less than 15μA,and the average equivalent series resistance(ESR)value of the product is less than that of 50 mΩ.
Polytetrafluoroethylene(PTEF)solution was used to pretreat the anodic surface of a Ta porous body formed by a tantalum oxide film(Ta2 O5),and non-conductive polymer interpenetrating network with many through holes was formed in the micro porous of tantalum anode.Then the chemical polymerization method was used to polymerize 3,4-ethylene glycol two oxygen thiophene(PEDT)in the interpenetrating network hole,so a conductive polymer composite flexible solid electrolyte layer is formed on the surface of Ta anode.The experimental results show that use 20% volume of PTEF water dispersions,a composite solid electrolyte layer with high mechanical strength would be coated on the surface of the tantalum anode,The average leakage current of the tantalum electrolytic capacitor is less than 15μA,and the average equivalent series resistance(ESR)value of the product is less than that of 50 mΩ.
引文
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[15]Yu Linpo,Chen Zheng.Attempts to improve the energy capacity of capacitive electrochemical energy storage devices[J].Journal of Electrochemistry,2017,23(05):533-547(in Chinese).余林颇,陈政.提高电容性电化学储能装置能量容量的一些尝试(英文)[J].电化学,2017,23(05):533-547.
[16]Wang Xuejing,Guo Zhengfei,Qu Jingming etal.In-situ characterization of electrochromism based on ITO/PEDOT:PSS towards preparation of high performance device[J].Chinese Physics B,2016,25(02):521-525.
[17]Li Jianxiong,Wang Jiong,Liu Anhua.Effect of EDOT solvent on molecular structures and properties of PEDOT synthesized by liquid phase depositional polymerization[J].Polymer Materials Science and Engineering,2016,32(09):7-14(in Chinese).李建雄,王炯,刘安华.单体溶剂对液相沉降聚合聚3,4-乙撑二氧噻吩分子结构及性能的影响[J].高分子材料科学与工程,2016,32(09):7-14.
[2]Xia Shuang,Xu Jianhua,Yang Yajie,et al.Research on improve production technology for performance of organic solid-electrolyte tantalum capacitor[J].Journal of Functional Materials,2012,43(5):587-589(in Chinese).夏双,徐建华,杨亚杰,等.改善有机片式固体钽电解电容器性能工艺研究[J].功能材料,2012,43(5):587-589.
[3]Ouyang J Y.“Secondary doping”methods to significantly enhance the conductivity of PEDOT∶PSS for its application as transparent electrode of optoelectronic devices[J].Displays,2013,34(5):423.
[4]Zhang Lin,Du Wenya,Amit Nautiya,et al.Recent progress on nanostructure conducting polymers and composites:synthesis,application and future aspects[J].Science China Materials,2018,61(03):303-352(in Chinese).张麟,杜文雅,Amit Nautiyal,等.纳米结构导电聚合物及其复合材料的研究进展:制备,应用和展望[J].中国材料科学,2018,61(03):303-352.
[5]Liu Jingzhen,Tu Shijian,Wang Yuechuan.Electrochemical synthesis of poly(3,4-ethylenedioxythiophene)in electrolyte aqueous[J].Materials Review,2011,25(5):65-68(in Chinese).刘景珍,涂世俭,王跃川.3,4-乙撑二氧噻吩水相的电化学聚合[J].材料导报B:研究篇,2011,25(5):65-68.
[6]Manisankar P,Vedhi C,Selvanathan G,et al.Electrochemical synthesis and characterization of novel electrochromic poly(3,4-ethylenedioxythiophene-co-diclofenac)with surfactants[J].Electrochimica Acta,2006,51(14):2964-2970.
[7]Zhang Meijuan,Li Jianxiong,Liu Anhua,et al.Preparation of PEDOT film by liquid phase depositional polymerization[J].Polymer Materials Science and Engineering,2013,29(4):129-132(in Chinese).张美娟,李建雄,刘安华,等.液相沉积聚合法制备的聚3,4-乙撑二氧噻吩(PEDOT)薄膜[J].高分子材料科学与工程,2013,29(4):129-132.
[8]LiGuojie.Conductive polymer composites and the study of their response behaviors to external fields[D].Zhengzhou:Zhengzhou University,2015(in Chinese).李国杰.导电高分子复合材料的导电网络结构调控及外场响应性能研究[D].郑州:郑州大学,2015.
[9]Xiao Yujuan,He Qiannan,Zhou Huanyu,et al.In situ polymerization of PEDOT:π-conjugated polyelectrolyte and application as hole transport layer in polymer solar cells[J].Acta Polymerica Sinica,2018(02):257-265(in Chinese).肖玉娟,何倩楠,周环宇,等.原位聚合聚(3,4-乙烯二氧噻吩):π共轭聚电解质应用于聚合物太阳能电池空穴传输层[J].高分子学报,2018(02):257-265.
[10]Lu Sheng.A preparation method of carbon nitride electrode material for capacitors[P].China patent:ZL201610716092.2,2018-4-06(in Chinese).陆胜.一种电容器用碳基氮化电极材料的制备方法[P].中国:发明专利,ZL201610716092.2,2018-4-06.
[11]Zhang Qingwei,Mi Jun,Yin Yalei.Preparation and properties of Poly(3,4-ethylenedioxythiophene)[J].Shandong Chemical Industry,2018,47(07):7-9(in Chinese).张庆伟,米俊,尹亚雷.聚(3,4-乙撑二氧噻吩)复合材料的制备及性能研究[J].山东化工,2018,47(07):7-9.
[12]Zhang Sihang,He Yongfeng,Fu Runfang,et al.Preparation and electrochromic properties of nano cellulose/poly(3,4-ethylenedioxythiophene)composite films[J].Chemical Journal of Chinese Universities,2017,38(06):1090-1098(in Chinese).张思航,何永锋,付润芳,等.纳米纤维素/聚3,4-乙撑二氧噻吩复合薄膜的制备及电致变色性能[J].高等学校化学学报,2017,38(06):1090-1098.
[13]Yang Wenyao,Li Jie,Gao Junhua,et al.Preparation and electrochemical properties of PEDOT/AC composites electrodes for supercapacitors[J].Journal of Functional Materials,2017,48(02):2005-20089(in Chinese).杨文耀,李杰,高君华,等.超级电容器用PEDOT/AC复合电极的制备及电化学性能[J].功能材料,2017,48(02):2005-2008.
[14]Lu Sheng.Preparation method of high conductivity flexible composite cathode electrolyte[P].China:Invention patent.ZL201410279939.6,2016-7-27(in Chinese).陆胜.高导电率柔性复合阴极电解质制备方法[P].中国:发明专利,ZL201410279939.6,2016-7-27.
[15]Yu Linpo,Chen Zheng.Attempts to improve the energy capacity of capacitive electrochemical energy storage devices[J].Journal of Electrochemistry,2017,23(05):533-547(in Chinese).余林颇,陈政.提高电容性电化学储能装置能量容量的一些尝试(英文)[J].电化学,2017,23(05):533-547.
[16]Wang Xuejing,Guo Zhengfei,Qu Jingming etal.In-situ characterization of electrochromism based on ITO/PEDOT:PSS towards preparation of high performance device[J].Chinese Physics B,2016,25(02):521-525.
[17]Li Jianxiong,Wang Jiong,Liu Anhua.Effect of EDOT solvent on molecular structures and properties of PEDOT synthesized by liquid phase depositional polymerization[J].Polymer Materials Science and Engineering,2016,32(09):7-14(in Chinese).李建雄,王炯,刘安华.单体溶剂对液相沉降聚合聚3,4-乙撑二氧噻吩分子结构及性能的影响[J].高分子材料科学与工程,2016,32(09):7-14.