界面法制备三维网状PPy-PEDOT共聚物膜及电容性能

doi:10.11868/j.issn.1001-4381.2018.000908

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摘要

制备具有多电子传输与多孔有序的结构电极是电化学储能技术创新发展的两个重要策略。本工作采用一种界面电化学聚合新法合成聚吡咯-聚3，4-乙撑二氧噻吩（PPy-PEDOT）共聚物薄膜材料。采用FTIR，XPS，EDX，SEM与电化学充放电测试对PPy-PEDOT共聚物膜的化学组成、分布、微观形貌及电容性能进行表征与测试。结果表明：PPy-PEDOT共聚物膜由PPy与PEDOT按一定比例组成，且分布均匀；SEM测试表明共聚物膜具有正反两面各异的特殊形貌，且有机相一侧呈三维网状多孔层状结构。电化学充放电测试表明，PPy-PEDOT共聚物膜表现出优异的超级电容器电极材料的特性，具有较高的比电容，较快的充放电速率与较好的循环稳定性。PPy与PEDOT共聚后实现二者性能互补，提高了共聚物膜的导电性，电荷迁移速率及稳定性，同时三维网状多孔层状结构也有助于充放电过程中电子离子的迁移，使得共聚物膜的储能性能显著提高。

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	李闽
	刘敏
	刘康

关键词 ：聚吡咯, PEDOT, 共聚物, 界面聚合, 超级电容器

Abstract：

Advances in multi-electron transfer materials and architectured electrodes are two important strategies for innovations in electrochemicalenergy storage. The attainment of both by interfacial electrodeposition of freestanding PPy-PEDOT copolymer films was reported. The composition of the copolymer was verified by FTIR and XPS spectra.The dispersion and microstructure of PPy and PEDOT were studied by EDX mapping and SEM. The capacitive performances of the copolymer films were studied by electrochemical measurements. The results show the copolymer film is composed of PPy and PEDOT with homogeneous distribution in a certain proportion.The SEM images show the film exhibits heterogeneous microstructure and has an open porous 3D network microstructure. Electrochemical characterization shows that the copolymer film is an excellent supercapacitor electrode material with high specific capacitance, good power capability and cycle performance. The multi-electron transfer nature of the copolymer, the copolymerization synergistic effects and the unique microstructure are responsible for the improved charge-discharge performances.

Key words： polypyrrole PEDOT copolymer interfacial synthesis supercapacitor

收稿日期: 2018-07-26 出版日期: 2019-09-18

中图分类号:

TB332

基金资助:湖北省自然科学基金项目(2018CFB139)

通讯作者: 李闽,刘康 E-mail: cherry1986222@163.com;14700241@qq.com

作者简介: 刘康(1982-), 男, 博士, 研究方向为信号处理, 联系地址:武汉经济技术开发区(汉南区)经信局C421(430056), E-mail:14700241@qq.com
李闽(1986-), 女, 高级工程师, 博士, 研究方向为高分子储能材料及电化学性能, 联系地址:湖北省武汉市汉阳区东风大道816号武汉商学院机电工程与汽车服务学院311室(430056), E-mail:cherry1986222@163.com

引用本文:

李闽, 刘敏, 刘康. 界面法制备三维网状PPy-PEDOT共聚物膜及电容性能[J]. 材料工程, 2019, 47(9): 123-131.
Min LI, Min LIU, Kang LIU. Preparation and capacitance properties of three-dimensional network PPy-PEDOT copolymer membranes by interface method. Journal of Materials Engineering, 2019, 47(9): 123-131.

链接本文:

http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2018.000908 或 http://jme.biam.ac.cn/CN/Y2019/V47/I9/123

Fig.1 动态固/液/液三相界域电化学聚合PPy-PEDOT共聚物膜过程

Fig.2 循环伏安法聚合导电聚合物的CV曲线
(a)PPy; (b)PEDOT; (c)PPy-PEDOT共聚物的CV曲线; (d)不同Py/EDOT比例下恒电位法聚合PPy-PEDOT共聚物的I-t曲线

Fig.3 纯PPy, PEDOT膜及单体浓度比为1:1下合成的PPy-PEDOT共聚物膜成分分析
(a)红外光谱；(b)XPS元素分析

Table 1 不同Py/EDOT比例下PPy-PEDOT共聚物膜元素分析数据

Fig.4 PPy-PEDOT复合薄膜的SEM图
(a)Py/EDOT比例为10:1；(b)Py/EDOT比例为1:1；(c)Py/EDOT比例为1:5;(1)复合膜正面(靠近水相一侧); (2)复合膜反面(靠近有机相一侧)

Fig.5 PPy-PEDOT共聚物膜表面元素分析EDX图
(a)正面；(b)反面

Fig.6 PPy-PEDOT共聚物膜电极循环伏安特性
(a)Py/EDOT比例为1:1时合成PPy-PEDOT共聚物膜不同扫描速率下的CV曲线；(b)50mV·s^-1下纯PPy膜，纯PEDOT膜及PPy-PEDOT共聚物膜的CV曲线；(c)不同扫描速率下纯PPy膜，纯PEDOT膜及PPy-PEDOT共聚物膜的比电容值

Fig.7 PPy-PEDOT共聚物膜电极恒流充放电曲线
(a)Py/EDOT比例为1:1时合成PPy-PEDOT共聚物膜不同电流密度下的恒流充放电曲线；(b)1A·g^-1下纯PPy膜及PPy-PEDOT共聚物膜恒流充放电曲线；(c)不同电流密度下纯PPy膜及PPy-PEDOT共聚物膜的比电容值

Fig.8 纯PPy与PPy-PEDOT共聚物膜循环寿命曲线

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