Classic density functional theory for designing supercapacitors

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

Abstract

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

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

CLC Number:

TQ028.8

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

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.

Figures/Tables 17

References 44

1	CHMIOLA J , YUSHIN G , GOGOTSI Y , et al . Anomalous increase in carbon capacitance at pore sizes less than 1 nanometer[J]. Science, 2006, 313: 1760-1763.
2	SIMON P , GOGOTSI Y . Materials for electrochemical capacitors[J]. Nat. Mater., 2008, 7: 845-854.
3	SIMON P , GOGOTSI Y . Capacitive energy storage in nanostructured carbon–electrolyte systems[J]. Acc. Chem. Res. ,2013, 46: 1094-1103.
4	VAN AKEN K L , BEIDAGHI M , GOGOTSIE Y . Formulation of ionic liquid electrolyte to expand the voltage window of supercapacitors[J]. Angew. Chem. Int. Ed., 2015, 54: 4806-4809.
5	LI W , ZHANG F , DOU Y , et al . A self-template strategy for the synthesis of mesoporous carbon nanofibers as advanced supercapacitor electrodes[J]. Advanced Energy Materials, 2011, 1: 382-386.
6	FEDOROV M V , KORNYSHEV A A . Ionic liquids at electrified interfaces[J]. Chem. Rev., 2014, 114: 2978-3036.
7	ZHONG C , DENG Y , HU W , et al . A review of electrolyte materials and compositions for electrochemical supercapacitors[J]. Chem. Soc. Rev., 2015, 44: 7484-7539.
8	ZHAN C , LIAN C , ZHANG Y , et al . Computational insights into materials and interfaces for capacitive energy storage[J]. Advanced Science ,2017, 4:1700059.
9	JIANG D , WU J . Microscopic insights into the electrochemical behavior of nonaqueous electrolytes in electric double-layer capacitors[J]. J. Phys. Chem. Lett., 2013, 4: 1260-1267.
10	JIANG D , JIN Z , HENDERSON D , et al . Solvent effect on the pore-size dependence of an organic electrolyte supercapacitor[J]. J. Phys. Chem. Lett., 2012, 3: 1727-1731.
11	LIAN C LIU K , VAN AKEN K , et al . Enhancing the capacitive performance of electric double-layer capacitors with ionic liquid mixtures[J]. ACS Energy Letters, 2016, 1:21-26.
12	LIAN C , JIANG D E , LIU H L , et al . A generic model for electric double layers in porous electrodes[J].PhysJ.Chem. C , 2016, 120:8704-8710.
13	EVANS R . Nature of the liquid-vapor interface and other topics in the statistical-mechanics of nonuniform, classical fluids[J]. Adv. Phys., 1979, 28:143-200.
14	EVANS R , OETTEL M , ROTH R , et al . New developments in classical density functional theory[J]. J. Phys-Condens Mat., 2016, 28: 240401.
15	HAGHMORADI A , WANG L , CHAPMAN W G . A density functional theory for colloids with two multiple bonding associating sites[J]. J. Phys-Condens Mat., 2016, 28: 244009.
16	WU J Z , LI Z D . Density-functional theory for complex fluids[J]. Annu. Rev. Phys. Chem., 2007, 58: 85-112.
17	LIAN C , CHEN X Q , ZHAO S L , et al . Substrate effect on the phase behavior of polymer brushes with lattice density functional theory[J]. Macromol. Theor. Simul., 2014, 23: 575-582.
18	PATRYKIEJEW A , SOKOLOWSKI S . Adsorption of associating fluids on solid surfaces: wetting transition from density functional theory[J]. The Journal of Physical Chemistry B, 1999, 103: 4466-4473.
19	TARAZONA P , EVANS R . A simple density functional theory for inhomogeneous liquids: wetting by gas at a solid-liquid interface[J]. Molecular Physics, 1984, 52: 847-857.
20	ROSENFELD Y . Free-dnergy model for the inhomogeneous hard-sphere fluid mixture and density-functional theory of freezing[J]. Phys. Rev. Lett. ,1989, 63: 980.
21	HAMMAWA H , HAMAD E Z . A simple and accurate mixture model[J]. Fluid Phase Equilibria, 1996, 122: 67-74.
22	ROTH R , EVANS R , LANG A , et al . Fundamental measure theory for hard-sphere mixtures revisited: the white bear version[J]. Journal of Physics: Condensed Matter, 2002, 14: 12063.
23	YU Y X , WU J Z . Structures of hard-sphere fluids from a modified fundamental-measure theory[J]. J. Chem. Phys. ,2002, 117:10156-10164.
24	YU Y X , WU J Z . A modified fundamental measure theory for spherical particles in microchannels[J]. J. Chem. Phys., 2003, 119: 2288-2295.
25	LIAN C , WANG L , CHEN X Q , et al . Modeling swelling behavior of thermoresponsive polymer brush with lattice density functional theory[J]. Langmuir, 2014, 30: 4040-4048.
26	LIAN C , LIU H L , HENDERSON D , et al . Can ionophobic nanopores enhance the energy storage capacity of electric-double-layer capacitors containing nonaqueous electrolytes? [J]. Journal of Physics: Condensed Matter, 2016, 28: 414005.
27	JIANG J , CAO D P , JIANG D E , et al . Time-dependent density functional theory for ion diffusion in electrochemical systems[J]. J.Phys. Condens. Matter, 2014, 26: 284102.
28	JIANG D E , JIN Z H , WU J Z . Oscillation of capacitance inside nanopores[J]. Nano Lett., 2011, 11: 5373-5377.
29	JIANG D E , WU J Z . Microscopic insights into the electrochemical behavior of nonaqueous electrolytes in electric double-layer capacitors[J].PhysJ. Chem. Lett. ,2013, 4:1260-1267.
30	LIAN C , GALLEGOS A , LIU H L , et al . Non-scaling behavior of electroosmotic flow in voltage-gated nanopores[J]. Phys. Chem. Chem. Phys., 2017, 19: 450-457.
31	LIAN C , JIANG D E , LIU H L , et al . A generic model for electric double layers in porous electrodes[J].PhysJ.Chem. C, 2016, 120:8704-8710.
32	LETCHWORTH-WEAVER K , ARIAS T . Joint density functional theory of the electrode-electrolyte interface: application to fixed electrode potentials, interfacial capacitances, and potentials of zero charge[J]. Physical Review B, 2012, 86: 075140.
33	ZHAN C , NEAL J , WU J , et al . Quantum effects on the capacitance of graphene-based electrodes[J].
	Phys J. . Chem. C, 2015, 119:22297-22303.
34	LIAN C , ZHAN C , JIANG D E , et al . Capacitive energy extraction by few-layer graphene electrodes[J].
	Phys J. . Chem. C, 2017, 121:14010-14018.
35	LIAN C , KONG X , LIU H L , et al . On the hydrophilicity of electrodes for capacitive energy extraction[J]. J. Phys.Condens. Matter, 2016, 28:464008.
36	VAN AKEN K L , Beidaghi M , Gogotsi Y . Formulation of ionic‐liquid electrolyte to expand the voltage window of supercapacitors[J]. Angew. Chem. Int. Ed., 2015, 54:4806-4809.
37	JIANG D E , WU J Z . Unusual effects of solvent polarity on capacitance for organic electrolytes in a nanoporous electrode[J]. Nanoscale, 2014, 6: 5545-5550.
38	LIAN C , ZHAO S L , LIU H L , et al . Time-dependent density functional theory for the charging kinetics of electric double layer containing room-temperature ionic liquids[J]. J. Chem. Phys., 2016, 145:204707.
39	LIAN C , LIU K , LIU H L , et al . Impurity effects on charging mechanism and energy storage of nanoporous supercapacitors[J].
	Phys J. . Chem. C, 2017, 121:14066-14072.
40	MA Z F, YUAN X , LI L , et al . A review of cathode materials and structures for rechargeable lithium-air batteries[J]. Energy Environ. Sci., 2015, 8: 2144-2198.
41	CHE H , CHEN S , XIE Y , et al . Electrolyte design strategies and research progress for room-temperature sodium-ion batteries[J]. Energy Environ. Sci., 2015, 10:1075-1101.
42	李作鹏，赵建国，温雅琼, 等 . 超级电容器电解质研究进展[J]. 化工进展, 2012, 31(8):1631-1640.
	LI Z P ， ZHAO J G , WEN Y Q , et al . Research progress of electrolytes in supercapacitors[J]. Chemical Industry and Engineering Progress, 2012, 31(8):1631-1640.
43	LIAN C , LIU H L , WU J Z . Ionic-liquid mixture expands the potential window and capacitance of a supercapacitor in tandem[J].
	Phys J. . Chem. C, 2018, 122:18304-18310.
44	LIAN C , SU H P , LIU H L , et al . Electrochemical behavior of nanoporous supercapacitors with oligomeric ionic liquids[J].
	Phys J. . Chem. C , 2018, 122:14402-14407.

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