高比能超级电容器:电极材料、电解质和能量密度限制原理

doi:10.11868/j.issn.1001-4381.2019.000721

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摘要

超级电容器是一种功率型储能器件，具有高功率密度和长循环寿命等优点。但是其能量密度很低，这限制了更宽范围的应用。本文首先介绍目前超级电容器工作原理，归纳总结了电极材料应具有的特点以及目前研究进展，然后总结了水系、有机系和离子液体电解质的特点及相关进展。最后指出了超级电容器能量密度限制原因和影响因素，并且从电极材料、电解质以及超级电容器结构三个方面出发，分析讨论超级电容器能量密度的提升措施。

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	郑俊生
	秦楠
	郭鑫
	金黎明
	ZhengJim P

关键词 ：超级电容器, 能量密度, 限制原理, 提升方法

Abstract：

Supercapacitors are power-type energy storage devices with high power density and long cycle life. However, the low energy density limits wider applications. In this paper, the working principle of supercapacitors was first introduced, and the characteristics of electrode materials needed and current progress were summarized. Then, the characteristics and related progress of aqueous, organic and ionic liquid electrolytes were introduced. Finally, the principle and the factors of energy density limitation of supercapacitors were pointed out, and the improvement methods were discussed from the aspects of electrode materials, electrolytes and the structure of supercapacitors, respectively.

Key words： supercapacitor energy density limitation principle improvement method

收稿日期: 2019-08-01 出版日期: 2020-09-17

中图分类号:

O646

基金资助:国家自然科学基金(51777140);上海市科学技术委员会科研计划项目(17DZ1200403);同济大学中央高校基本科研业务基金(22120180519);同济大学中央高校基本科研业务基金(22120180308)

通讯作者: 郑俊生 E-mail: jszheng@tongji.edu.cn

作者简介: 郑俊生(1979-), 男, 副研究员, 博士, 研究方向为车用新能源, 联系地址:上海市嘉定区安亭镇曹安公路4800号同济大学新能源工程中心411室(201804), E-mail:jszheng@tongji.edu.cn

引用本文:

郑俊生, 秦楠, 郭鑫, 金黎明, ZhengJim P. 高比能超级电容器:电极材料、电解质和能量密度限制原理[J]. 材料工程, 2020, 48(9): 47-58.
Jun-sheng ZHENG, Nan QIN, Xin GUO, Li-ming JIN, Jim P Zheng. High energy density supercapacitors: electrode material, electrolyte and energy density limitation principle. Journal of Materials Engineering, 2020, 48(9): 47-58.

链接本文:

http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2019.000721 或 http://jme.biam.ac.cn/CN/Y2020/V48/I9/47

Fig.1 超级电容器技术储能路线图

Fig.2 描述双电层电容器储能机理的模型^[5]
(a)Helmholtz双电层模型; (b)GC双电层模型; (c)Stern双电层模型

Fig.3 描述多种孔隙状态的纳米多孔碳超级电容器的通用模型^[9]

Fig.4 双电层电容器结构示意图^[10]

Fig.5 水系对称型超级电容器的电化学稳定区间^[49]
(a)5 mol·L^-1 LiCl电解液；(b)0.5 mol·L^-1 H₂SO₄电解液；(c)1 mol·L^-1 KOH电解液

Fig.6 α=1/2时电解质不同盐浓度的电容器的能量密度与比电容之间的关系^[57]

Fig.7 归一化电容与孔径尺寸和离子尺寸比例的关系^[24]
(a)点数据图；(b)标准化电容图

Fig.8 通过电极电容的不均衡调节正负极电位窗口，增加工作电压^[64](a)和通过表面电荷修饰改变开路电压，可控调节电极的工作电压范围^[49](b)的示意图

Fig.9 未完全利用稳定电位区间的有机碳基超级电容器示例及改进方法示意图
(a)EDLC在施加不同电压时释放气体示意图^[53]；(b)正极电位先达到稳定电位区间界限的对称超级电容器；(c)负极电位先达到稳定电位区间界限的对称超级电容器；(d)完全利用稳定电位区间的非对称超级电容器

Fig.10 充电过程，锂离子电容器和双电层电容器正负极电位变化示意图^[16]

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