经典密度泛函理论在双电层超级电容器研究中的应用

doi:10.16085/j.issn.1000-6613.2018-1014

化工进展 ›› 2019, Vol. 38 ›› Issue (01): 244-260.DOI: 10.16085/j.issn.1000-6613.2018-1014

经典密度泛函理论在双电层超级电容器研究中的应用

练成(),刘洪来()

华东理工大学化学与分子工程学院，国家化学工程重点实验室，上海200237

收稿日期:2018-05-15 修回日期:2018-09-19 出版日期:2019-01-05 发布日期:2019-01-05
通讯作者: 刘洪来
作者简介:练成（1989—），男，博士，研究方向为表界面热力学。E-mail：<email>liancheng@ecust.edu.cn</email>。|刘洪来，教授，博士生导师，研究方向为界面科学与热力学。E-mail：<email>hlliu@ecust.edu.cn</email>。
基金资助:
国家自然科学基金创新群体项目(51621002);国家自然科学基金(21808055，21476072);博新计划(BX201700076);华东理工大学基本科研业务费青年教师探索研究基金(222201814016);中国博士后科学基金(2017M620137);上海市青年科技英才扬帆计划(18YF1405400);国家自然科学基金创新群体项目（51621002）；国家自然科学基金（21808055，21476072）；博新计划（BX201700076）；华东理工大学基本科研业务费青年教师探索研究基金（222201814016）；中国博士后科学基金（2017M620137）；上海市青年科技英才扬帆计划（18YF1405400）。

Classic density functional theory for designing supercapacitors

Cheng LIAN(),Honglai LIU()

State Key Laboratory of Chemical Engineering and School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2018-05-15 Revised:2018-09-19 Online:2019-01-05 Published:2019-01-05
Contact: Honglai LIU

摘要/Abstract

摘要：

提高储能密度是目前超级电容器研究的重点，它取决于电极材料与电解液界面结构。本文介绍了经典密度泛函理论（CDFT）研究固液界面结构的基本原理以及在多孔电极材料中电解液溶液的热力学和动力学性质研究等进展。CDFT是一种基于统计力学的理论方法，被广泛应用于表界面效应、吸附、溶解等研究，在保证相同计算精度的前提下，具有比分子模拟更高的计算效率。CDFT可以系统地研究多孔材料孔径、孔几何形貌、表面官能团，电解液离子大小、化合价、组成以及溶剂种类、浓度等因素对超级电容器性能的影响，进一步发展考虑反应-传递性质的CDFT，可以为设计新型电极材料和筛选电解液提供理论依据。

关键词: 超级电容器, 多孔电极, 电解质, 双电层, 经典密度泛函理论

Abstract:

The design of supercapacitor with high energy density requires a deep understanding of the contribution factors of the total capacitance. This article reviews the recent progress on predicting the capacitive performance of supercapacitors by using classical density functional theory (CDFT). Comparing to the conventional molecular simulations, the CDFT is superior in calculation speed, especially for electrolytes in porous electrodes. CDFT could be developed and applied to study the electrode/electrolyte interface behaviors, to understand the pore size effect, curvature effect, and the surface modification of porous materials and the electrolytes parts (the concentration effect, the solvent and impurity effect, and the ionic liquid mixture effect) on the capacitive performance. Further development of CDFT for electrode/electrolyte interface would allow researchers to design better supercapacitors.

Key words: supercapacitor, porous electrode materials, electrolyte, electric double layer, classical density functional theory

中图分类号:

TQ028.8

练成, 刘洪来. 经典密度泛函理论在双电层超级电容器研究中的应用[J]. 化工进展, 2019, 38(01): 244-260.

Cheng LIAN, Honglai LIU. Classic density functional theory for designing supercapacitors[J]. Chemical Industry and Engineering Progress, 2019, 38(01): 244-260.

图/表 17

图1 超级电容器模型

图2 离子在电极表面和孔道中的分布

图3 电容随着单孔孔径的变化

图4 电容随着平均孔径的变化

图5 不同材料孔道中的电导以及电导率随电解液浓度以及纳米孔道孔径的变化

图6 不同曲率下凹面和凸面电容随着电压的变化

图7 材料表面含氧基团对电化学性能的影响

图8 对离子的亲疏性不同的纳米孔道中离子数密度、微分电容以及能量密度与电势的关系

图9 量子电容的影响

图10 不同浓度电解液对应的微分电容随电压(ψ)的变化

图11 计算的积分电容和实验所得电容与组成x之间的关系

图12 离子液体在带正电电极表面的密度分布

图13 有无溶剂两种情况下电容随着孔径的变化

图14 电容随着溶剂种类的变化

图15 电极表面电荷密度（Qσ 2/e）随着约化时间（t/τD）的变化

图16 含有不同杂质的离子液体在纳米孔中的粒子数(N i)随电势(ψ)的变化

图17 杂质不同对超级电容器电容以及能量密度与电势关系的影响

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经典密度泛函理论在双电层超级电容器研究中的应用

Classic density functional theory for designing supercapacitors

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