超级电容器自放电的研究进展

doi:10.19799/j.cnki.2095-4239.2021.0688

储能科学与技术 ›› 2022, Vol. 11 ›› Issue (7): 2114-2125.doi: 10.19799/j.cnki.2095-4239.2021.0688

超级电容器自放电的研究进展

王宇作¹^,²(), 卢颖莉², 邓苗³, 杨斌⁴, 于学文², 荆葛², 阮殿波⁵^,⁶()

^1.天津大学化工学院，天津 300072
^2.宁波中车新能源科技有限公司，浙江宁波 315112
^3.中国人民解放军95979部队，山东泰安 271207
^4.宁波瞬能科技有限公司，浙江
^5.宁波 315048，宁波大学，先进储能技术与装备研究院，浙江宁波 315211
^6.清华大学材料学院，北京 100084

收稿日期:2021-12-20 修回日期:2021-12-29 出版日期:2022-07-05 发布日期:2022-06-29
通讯作者: 阮殿波 E-mail:396755221@qq.com;ruandianbo@nbu.edu.cn
作者简介:王宇作（1990—），男，博士，研究方向为电化学储能，E-mail：396755221@qq.com；
基金资助:
轨道交通车辆制动能量回馈关键技术(2019B10045)

Research progress of self-discharge in supercapacitors

Yuzuo WANG¹^,²(), Yinli LU², Miao DENG³, Bin YANG⁴, Xuewen YU², Ge JIN², Dianbo RUAN⁵^,⁶()

^1.School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
^2.Ningbo CRRC New Energy Technology Co. , Ltd. , Ningbo 315112, Zhejiang, China
^3.Unit 95979 of the PLA, Tai'an 271207, Shandong, China
^4.Ningbo Shunneng Technology Co. , Ltd. , Ningbo 315048, Zhejiang, China
^5.Ningbo University, Advanced Research Institute for Energy Storage Technology and Equipment, Ningbo 315211, Zhejiang, China
^6.School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China

Received:2021-12-20 Revised:2021-12-29 Online:2022-07-05 Published:2022-06-29
Contact: Dianbo RUAN E-mail:396755221@qq.com;ruandianbo@nbu.edu.cn

摘要/Abstract

摘要：

自放电是评价超级电容器性能的重要指标之一，显著影响超级电容器在实际使用过程中的能量转换效率。理解超级电容器的自放电机理，建立准确的自放电模型，从而开发针对性的改进方法，对提高超级电容器的实用性至关重要。然而，当前大量的研究工作集中于提高超级电容器的能量密度和功率密度，对其自放电性能的关注较少。因此，本文综述了近年来超级电容器自放电研究工作的进展，着重介绍了电荷再分布、活化控制、扩散控制及电势驱动等自放电机制的数学模型及其影响因素，并从充电协议、表面化学改性、电极包覆、电解液/隔膜改性等方面总结了当前的自放电抑制策略，以期促进相关研究方向的发展。本文指出未来相关工作应在三个方面展开：首先，需要根据不同的应用需求建立完善的自放电评价体系；其次，需要将自放电的仿真模拟与先进的表征技术相结合，建立不同自放电机制的准确识别方法，并对其起因进行追溯；最后，需要根据自放电机制的不同，发展针对性的优化方法，实现自放电和其他电化学性能的同时优化。

关键词: 超级电容器, 自放电, 多孔碳, 双电层

Abstract:

Having a substantial impact on the energy conversion efficiency of supercapacitors, self-discharge is an essential metric to consider when evaluating their performance. Understanding the self-discharge mechanism, creating realistic simulation models, and designing optimal procedures are all necessary for supercapacitors to be practical. However, many types of research were just concentrated on the improvement of other parameters, e.g., energy/power density and lifespan. Less attention has been paid to the self-discharge performance of supercapacitors. Consequently, the progress of supercapacitor self-discharge research in recent years is discussed in this work to support the growth of self-discharge research. The influencing factors and mathematic models for different self-discharge mechanisms (charge redistribution, activation control, diffusion control, and potential driving) are summarized in detail. Self-discharge limitation approaches using several tactics (charging proposal, surface-chemistry alteration, electrode coating, and functional electrolyte/separator) are also discussed. This paper emphasizes that the corresponding works should be performed in three aspects in the future: First, it is necessary to develop an accurate evaluation system of self-discharge according to various application requirements. Second, to build a reliable identification technique for distinct self-discharge processes and identify their origins, simulation approaches must be combined with modern characterization technologies. Finally, it is necessary to establish specific optimization methods according to the different self-discharge mechanisms to achieve the simultaneous optimization of self-discharge and other electrochemical performances.

Key words: supercapacitor, self-discharge, porous carbon, electric double-layer

中图分类号:

TM 911

王宇作, 卢颖莉, 邓苗, 杨斌, 于学文, 荆葛, 阮殿波. 超级电容器自放电的研究进展[J]. 储能科学与技术, 2022, 11(7): 2114-2125.

Yuzuo WANG, Yinli LU, Miao DENG, Bin YANG, Xuewen YU, Ge JIN, Dianbo RUAN. Research progress of self-discharge in supercapacitors[J]. Energy Storage Science and Technology, 2022, 11(7): 2114-2125.

图/表 1

参考文献 60

1	YANG Z G, ZHANG J L, KINTNER-MEYER M C W, et al. Electrochemical energy storage for green grid[J]. Chemical Reviews, 2011, 111(5): 3577-3613.
2	YANG Z G, LIU J, BASKARAN S, et al. Enabling renewable energy—and the future grid—with advanced electricity storage[J]. JOM, 2010, 62(9): 14-23.
3	CHOI J W, AURBACH D. Promise and reality of post-lithium-ion batteries with high energy densities[J]. Nature Reviews Materials, 2016, 1: 16013.
4	SIMON P, GOGOTSI Y. Perspectives for electrochemical capacitors and related devices[J]. Nature Materials, 2020, 19(11): 1151-1163.
5	NOORI A, EL-KADY M F, RAHMANIFAR M S, et al. Towards establishing standard performance metrics for batteries, supercapacitors and beyond[J]. Chemical Society Reviews, 2019, 48(5): 1272-1341.
6	IKE I S, SIGALAS I, IYUKE S. Understanding performance limitation and suppression of leakage current or self-discharge in electrochemical capacitors: A review[J]. Physical Chemistry Chemical Physics, 2016, 18(2): 661-680.
7	LIU K L, YU C, GUO W, et al. Recent research advances of self-discharge in supercapacitors: Mechanisms and suppressing strategies[J]. Journal of Energy Chemistry, 2021, 58: 94-109.
8	SMITH P H, TRAN T N, JIANG T L, et al. Lithium-ion capacitors: Electrochemical performance and thermal behavior[J]. Journal of Power Sources, 2013, 243: 982-992.
9	ZHONG C, DENG Y D, HU W B, et al. A review of electrolyte materials and compositions for electrochemical supercapacitors[J]. Chemical Society Reviews, 2015, 44(21): 7484-7539.
10	RAZA W, ALI F, RAZA N, et al. Recent advancements in supercapacitor technology[J]. Nano Energy, 2018, 52: 441-473.
11	SUN X Z, AN Y B, GENG L B, et al. Leakage Current and self-discharge in lithium-ion capacitor[J]. Journal of Electroanalytical Chemistry, 2019, 850: 113386.
12	ZAKHIDOV A A, SUH D S, KUZNETSOV A A, et al. Electrochemically tuned properties for electrolyte-free carbon nanotube sheets[J]. Advanced Functional Materials, 2009, 19(14): 2266-2272.
13	CONWAY B E, PELL W G, LIU T C. Diagnostic analyses for mechanisms of self-discharge of electrochemical capacitors and batteries[J]. Journal of Power Sources, 1997, 65(1/2): 53-59.
14	DE LEVIE R. On porous electrodes in electrolyte solutions[J]. Electrochimica Acta, 1963, 8(10): 751-780.
15	MADABATTULA G, KUMAR S. Insights into charge-redistribution in double layer capacitors[J]. Journal of the Electrochemical Society, 2018, 165(3): A636-A649.
16	HAO C L, WANG X F, YIN Y J, et al. Analysis of charge redistribution during self-discharge of double-layer supercapacitors[J]. Journal of Electronic Materials, 2016, 45(4): 2160-2171.
17	GRAYDON J W, PANJEHSHAHI M, KIRK D W. Charge redistribution and ionic mobility in the micropores of supercapacitors[J]. Journal of Power Sources, 2014, 245: 822-829.
18	KAUS M, KOWAL J, SAUER D U. Modelling the effects of charge redistribution during self-discharge of supercapacitors[J]. Electrochimica Acta, 2010, 55(25): 7516-7523.
19	陈雪龙, 张希, 许传华, 等. 大容量动力型超级电容器存储性能[J]. 储能科学与技术, 2021, 10(1): 198-201.
	CHEN X L, ZHANG X, XU C H, et al. Storage performance of large-capacitance power supercapacitor[J]. Energy Storage Science and Technology, 2021, 10(1): 198-201.
20	MADABATTULA G, KUMAR S. Model and measurement based insights into double layer capacitors: Voltage-dependent capacitance and low ionic conductivity in pores[J]. Journal of the Electrochemical Society, 2020, 167(8): 080535.
21	BLACK J M, ANDREAS H A. Pore shape affects spontaneous charge redistribution in small pores[J]. The Journal of Physical Chemistry C, 2010, 114(27): 12030-12038.
22	BU Y F, SUN T, CAI Y J, et al. Compressing carbon nanocages by capillarity for optimizing porous structures toward ultrahigh-volumetric-performance supercapacitors[J]. Advanced Materials, 2017, 29(24): 1700470.
23	贾志军, 王俊, 王毅. 超级电容器电极材料的研究进展[J]. 储能科学与技术, 2014, 3(4): 322-338.
	JIA Z J, WANG J, WANG Y. Research progress of the electrode materials for electrochemical capacitors[J]. Energy Storage Science and Technology, 2014, 3(4): 322-338.
24	ANDREAS H A. Self-discharge in electrochemical capacitors: A perspective article[J]. Journal of the Electrochemical Society, 2015, 162(5): A5047-A5053.
25	OICKLE A M, TOM J, ANDREAS H A. Carbon oxidation and its influence on self-discharge in aqueous electrochemical capacitors[J]. Carbon, 2016, 110: 232-242.
26	KIERZEK K, FRACKOWIAK E, LOTA G, et al. Electrochemical capacitors based on highly porous carbons prepared by KOH activation[J]. Electrochimica Acta, 2004, 49(4): 515-523.
27	LIU T C, PELL W G, CONWAY B E. Self-discharge and potential recovery phenomena at thermally and electrochemically prepared RuO₂ supercapacitor electrodes[J]. Electrochimica Acta, 1997, 42(23/24): 3541-3552.
28	YANG H Z, ZHANG Y. Self-discharge analysis and characterization of supercapacitors for environmentally powered wireless sensor network applications[J]. Journal of Power Sources, 2011, 196(20): 8866-8873.
29	RICKETTS B W, TON-THAT C. Self-discharge of carbon-based supercapacitors with organic electrolytes[J]. Journal of Power Sources, 2000, 89(1): 64-69.
30	HESS L H, WITTSCHER L, BALDUCCI A. The impact of carbonate solvents on the self-discharge, thermal stability and performance retention of high voltage electrochemical double layer capacitors[J]. Physical Chemistry Chemical Physics, 2019, 21(18): 9089-9097.
31	KAZARYAN S A, LITVINENKO S V, KHARISOV G G. Self-discharge of heterogeneous electrochemical supercapacitor of PbO₂∣H₂SO₄∣C related to manganese and titanium ions[J]. Journal of the Electrochemical Society, 2008, 155(6): A464.
32	OICKLE A M, ANDREAS H A. Examination of water electrolysis and oxygen reduction as self-discharge mechanisms for carbon-based, aqueous electrolyte electrochemical capacitors[J]. The Journal of Physical Chemistry C, 2011, 115(10): 4283-4288.
33	ZHANG W, YANG W, ZHOU H H, et al. Self-discharge of supercapacitors based on carbon nanotubes with different diameters[J]. Electrochimica Acta, 2020, 357: 136855.
34	ZHANG Q, RONG J P, MA D S, et al. The governing self-discharge processes in activated carbon fabric-based supercapacitors with different organic electrolytes[J]. Energy & Environmental Science, 2011, 4(6): 2152.
35	ZHANG Q, RONG J P, WEI B Q. A divided potential driving self-discharge process for single-walled carbon nanotube based supercapacitors[J]. RSC Advances, 2011, 1(6): 989.
36	LAHEÄÄR A, ARENILLAS A, BÉGUIN F. Change of self-discharge mechanism as a fast tool for estimating long-term stability of ionic liquid based supercapacitors[J]. Journal of Power Sources, 2018, 396: 220-229.
37	JAMIESON L, ROY T, WANG H Z. Postulation of optimal charging protocols for minimal charge redistribution in supercapacitors based on the modelling of solid phase charge density[J]. Journal of Energy Storage, 2021, 33: 102075.
38	ZHANG Q, CAI C, QIN J W, et al. Tunable self-discharge process of carbon nanotube based supercapacitors[J]. Nano Energy, 2014, 4: 14-22.
39	WANG J, DING B, HAO X D, et al. A modified molten-salt method to prepare graphene electrode with high capacitance and low self-discharge rate[J]. Carbon, 2016, 102: 255-261.
40	YUAN S T, HUANG X H, WANG H, et al. Structure evolution of oxygen removal from porous carbon for optimizing supercapacitor performance[J]. Journal of Energy Chemistry, 2020, 51: 396-404.
41	HE Y T, ZHANG Y H, LI X F, et al. Capacitive mechanism of oxygen functional groups on carbon surface in supercapacitors[J]. Electrochimica Acta, 2018, 282: 618-625.
42	DAVIS M A, ANDREAS H A. Identification and isolation of carbon oxidation and charge redistribution as self-discharge mechanisms in reduced graphene oxide electrochemical capacitor electrodes[J]. Carbon, 2018, 139: 299-308.
43	MISHRA R K, CHOI G J, SOHN Y, et al. Nitrogen-doped reduced graphene oxide as excellent electrode materials for high performance energy storage device applications[J]. Materials Letters, 2019, 245: 192-195.
44	LIU D, FU C P, ZHANG N S, et al. Porous nitrogen-doped graphene for high energy density supercapacitors in an ionic liquid electrolyte[J]. Journal of Solid State Electrochemistry, 2017, 21(3): 759-766.
45	MISHRA R K, CHOI G J, SOHN Y, et al. A novel RGO/N-RGO supercapacitor architecture for a wide voltage window, high energy density and long-life via voltage holding tests[J]. Chemical Communications (Cambridge, England), 2020, 56(19): 2893-2896.
46	TEVI T, YAGHOUBI H, WANG J, et al. Application of poly (p-phenylene oxide) as blocking layer to reduce self-discharge in supercapacitors[J]. Journal of Power Sources, 2013, 241: 589-596.
47	WANG Y Z, SHAN X Y, WANG D W, et al. Mitigating self-discharge of carbon-based electrochemical capacitors by modifying their electric-double layer to maximize energy efficiency[J]. Journal of Energy Chemistry, 2019, 38: 214-218.
48	GANDLA D, SONG G H, WU C R, et al. Atomic layer deposition (ALD) of alumina over activated carbon electrodes enabling a stable 4 V supercapacitor operation[J]. ChemistryOpen, 2021, 10(4): 402-407.
49	CHUNG J, PARK H, JUNG C. Electropolymerizable isocyanate-based electrolytic additive to mitigate diffusion-controlled self-discharge for highly stable and capacitive activated carbon supercapacitors[J]. Electrochimica Acta, 2021, 369: 137698.
50	GE K K, LIU G M. Suppression of self-discharge in solid-state supercapacitors using a zwitterionic gel electrolyte[J]. Chemical Communications (Cambridge, England), 2019, 55(50): 7167-7170.
51	WANG Z X, CHU X, XU Z, et al. Extremely low self-discharge solid-state supercapacitors via the confinement effect of ion transfer[J]. Journal of Materials Chemistry A, 2019, 7(14): 8633-8640.
52	WANG H Y, ZHOU Q Q, YAO B W, et al. Suppressing the self-discharge of supercapacitors by modifying separators with an ionic polyelectrolyte[J]. Advanced Materials Interfaces, 2018, 5(10): 1701547.
53	ZHAO C Y, SUN X D, LI W S, et al. Reduced self-discharge of supercapacitors using piezoelectric separators[J]. ACS Applied Energy Materials, 2021, 4(8): 8070-8075.
54	WANG K P, YAO L L, JAHON M, et al. Ion-exchange separators suppressing self-discharge in polymeric supercapacitors[J]. ACS Energy Letters, 2020, 5(10): 3276-3284.
55	SUN X Z, ZHANG X, ZHANG H T, et al. Application of a novel binder for activated carbon-based electrical double layer capacitors with nonaqueous electrolytes[J]. Journal of Solid State Electrochemistry, 2013, 17(7): 2035-2042.
56	AVIREDDY H, BYLES B W, PINTO D, et al. Stable high-voltage aqueous pseudocapacitive energy storage device with slow self-discharge[J]. Nano Energy, 2019, 64: 103961.
57	HAQUE M, LI Q, SMITH A D, et al. Self-discharge and leakage current mitigation of neutral aqueous-based supercapacitor by means of liquid crystal additive[J]. Journal of Power Sources, 2020, 453: 227897.
58	LIU M Y, XIA M Y, QI R J, et al. Lyotropic liquid crystal as an electrolyte additive for suppressing self-discharge of supercapacitors[J]. ChemElectroChem, 2019, 6(9): 2531-2535.
59	XIA M Y, NIE J H, ZHANG Z L, et al. Suppressing self-discharge of supercapacitors via electrorheological effect of liquid crystals[J]. Nano Energy, 2018, 47: 43-50.
60	HUANG Z D, WANG T R, SONG H, et al. Effects of anion carriers on capacitance and self-discharge behaviors of zinc ion capacitors[J]. Angewandte Chemie International Edition, 2021, 60(2): 1011-1021.

类型	电荷再分布		活化控制		扩散控制		电势驱动
线性关系	V～ln(t)		V～ln(t)		V～t^1/2		ln(V)～t
特征曲线
驱动力	电场		电场(过电势)		浓度梯度		电场
起源	非均态充电		电化学反应		电化学反应		欧姆泄漏
影响因素	充电协议	充电电压、充电电流、充电历史、工作温度	充电协议	充电电压、工作温度	充电协议	充电电压、工作温度	充电协议	充电电压、工作温度
	材料	电极材料(孔结构)、电解液(离子电导率)	材料	电极(活性位点)、电解液(分解电势)	材料	电极(孔结构、官能团)、电芯(厚度)	材料	电极(官能团)、电芯(结构缺陷)
	杂质	/	杂质	有机电解液中的痕量水	杂质	金属离子、H₂O₂、O₂	杂质	/

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超级电容器自放电的研究进展

Research progress of self-discharge in supercapacitors

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