离子液体型超级电容器软包高温老化性能评测研究

doi:10.11949/0438-1157.20211181

摘要/Abstract

摘要：

构筑了介孔炭，离子液体（EMIMBF₄）与泡沫铝极片结构的超级电容器软包（容量为40 F），评测了其在2.7 V，65℃，1500 h老化实验中的性能。利用恒流充放电、恒流-恒压充放电模式评测，该电容器经过连续1500 h的高温处理后电容值衰减约10%，内阻增加比例低于40%。与传统的乙腈基电解液软包对比，虽然乙腈基软包起始内阻低，但产气多，且高温循环条件下容量衰减比例和内阻增加比例均劣于离子液体基电解液。上述对比说明，离子液体基电解液在泡沫铝三维导电导热结构的配合下，具有了良好的长周期循环性能。同时，由于其无毒性，可以用于封闭的楼宇空间或其他场所，提供本质安全性。

关键词: 离子液体, 超级电容器, 高温老化, 长寿命评价

Abstract:

In this paper, a pouch supercapacitor with a structure of mesoporous carbon, ionic liquid (EMIMBF₄) and aluminum foam (capacity 40 F) was constructed, and its performance in the 2.7 V, 65℃, 1500 h aging experiment was evaluated. The capacitance of the supercapacitor attenuates about 10% and the internal resistance increases less than 40% after the 1500 h aging. Its performance is compared with the conventional acetonitrile-based pouch. Although the latter exhibits low initial internal resistance, gases in large amounts are produced and the capacitance attenuation ratio and the internal resistance increase ratio are higher under the high temperature cycling condition, compared to the ionic liquid-based pouch. The above comparison shows that ionic liquid-based electrolyte exhibits excellent cycling performance under the assistance of three dimensional conductive and thermal conductivity structure of aluminum foam. In addition, the advantage of non-toxic, low volatile point of ionic liquids would provide the intrinsic safety as used in enclosed spaces, such as in the elevators of skyscrapers.

Key words: ionic liquid, supercapacitor, high temperature aging, cycling life evaluation

中图分类号:

TQ 152

叶珍珍, 陈鑫祺, 汪剑, 李博凡, 崔超婕, 张刚, 钱陆明, 金鹰, 骞伟中. 离子液体型超级电容器软包高温老化性能评测研究[J]. 化工学报, 2021, 72(12): 6351-6360.

Zhenzhen YE, Xinqi CHEN, Jian WANG, Bofan LI, Chaojie CUI, Gang ZHANG, Luming QIAN, Ying JIN, Weizhong QIAN. Evaluation of aging performance under high temperature of ionic liquid-based pouch supercapacitor[J]. CIESC Journal, 2021, 72(12): 6351-6360.

图/表 9

图1 介孔炭的基本特性表征。(a)和(b)为材料的低倍和高倍扫描电镜照片；(c)和(d)为材料的氮气吸脱附曲线和孔径分布

Fig.1 Basic characterization of mesoporous carbon. Low (a) and high (b) magnification SEM images of the material; Nitrogen absorption and desorption curves (c) and pore size distribution (d) of the material

图2 三维通孔泡沫铝集流体的光学照片(a)；介孔炭与泡沫铝集流体构建的复合极片(b)；介孔炭颗粒在泡沫铝突起表面的附着情况(c)

Fig.2 Optical photograph of 3D through-hole aluminum foam current collector (a); Mesoporous carbon and aluminum foam composite electrode (b); Adhesion of mesoporous carbon particles on the protuberant surface of aluminum foam (c)

图3 介孔炭-EMIMBF4-泡沫铝体系的基本电化学测试。(a)循环伏安曲线；(b)电化学阻抗谱图；(c)恒流充放电曲线和(d)恒流-恒压充放电曲线

Fig.3 Basic electrochemical tests of mesoporous carbon-EMIMBF4-Al foam system. CV curves (a); EIS spectra (b); Constant current charge-discharge curve (c) and constant current-constant voltage charge-discharge curve (d)

图4 介孔炭-TEABF4/ACN-泡沫铝体系的基本电化学测试。(a)循环伏安曲线；(b)电化学阻抗谱图；(c)恒流充放电曲线和(d)恒流-恒压充放电曲线

Fig.4 Basic electrochemical tests of mesoporous carbon-TEABF4/ACN-Al foam system. CV curve (a); EIS spectra (b); Constant current charge-discharge curve (c) and constant current - constant voltage charge-discharge curve (d)

图5 介孔炭-EMIMBF4-泡沫铝体系的高温长时间测试。(a)恒流充放电曲线和(b)恒流-恒压充放电曲线；(c)电化学阻抗谱图；(d)循环伏安曲线

Fig.5 Long cycling test of mesoporous carbon-EMIMBF4-Al foam system at high temperature. Constant current charge-discharge curves (a) and constant current-constant voltage charge-discharge curves (b); EIS spectra (c); CV curves (d)

图6 介孔炭-TEABF4/ACN-泡沫铝体系的高温长时间测试。(a)恒流充放电曲线和(b)恒流-恒压充放电曲线；(c)电化学阻抗谱图；(d)循环伏安曲线

Fig.6 Long cycling test of mesoporous carbon-TEABF4/ACN-Al foam system at high temperature. Constant current charge-discharge curves (a) and constant current-constant voltage charge-discharge curves (b); EIS spectra (c); CV curves (d)

图7 EMIBF4 和TEABF4/ACN两体系的高温老化数据对比。(a)器件30 ms电压降值比较；(b)器件30 ms电阻值和(c)归一化比较；(d)恒流充放电比容量和(e)恒流-恒压充放电比容量进行归一化比较

Fig.7 Comparison of high temperature aging performance between EMIMBF4 and TEABF4/ACN systems. Comparison of 30 ms voltage drop of devices (a); Comparison of 30 ms resistance values (b) and ratio of resistance change (c); Comparison of the ratio of the specific capacitance change by the constant current charge-discharge mode (d) and the constant current-constant voltage charge-discharge mode (e)

图8 EMIMBF4和TEABF4/ACN两体系的高温老化过程产气对比

Fig.8 Comparison of gas production during high temperature aging of EMIMBF4 and TEABF4/ACN systems

图9 介孔炭-EMIMBF4-泡沫铝和介孔炭-TEABF4/ACN-泡沫铝两体系在高温老化前(a)、后(b)的能量密度与功率密度的比较；随着高温老化的进行EMIMBF4软包(c)、TEABF4/ACN软包(d)的能量密度与功率密度的变化趋势

Fig.9 Comparison of energy density and power density of mesoporous carbon-EMIMBF4-Al foam and mesoporous carbon-TEABF4/ACN-Al foam before (a) and after (b) high temperature aging; The changing trend of energy density and power density of EMIMBF4 pouch (c) and TEABF4/ACN pouch (d) with high temperature aging

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