Research progress on failure mechanism of electrochemical double layer capacitors

doi:10.11949/0438-1157.20240886

Abstract

Abstract:

Electrochemical double layer capacitor (EDLC) has attracted much attention due to its high power density, long cycle life and rapid charging capacity. However, the stability and reliability of EDLC are critical for practical applications. To improve the stability and extend life, it is important to understand the mechanism of performance attenuation and failure. This paper discusses the failure criteria of EDLC and methods for monitoring and in-situ electrochemical characterization of performance degradation. By reviewing research progress on the failure of EDLC, it focuses on key components such as electrode materials, electrolyte, electrode/electrolyte interface and current collector, with the purpose of revealing the failure phenomena and mechanisms in different systems. Finally, we look forward to the development direction and challenges of high stability EDLC, emphasizing the development and characteristics of new materials, and providing strategies for performance optimization and application expansion.

Key words: failure mechanism, failure criteria, carbon electrode, organic electrolyte, electrode/electrolyte interface, current collector

摘要：

电化学双电层电容器（electrochemical double layer capacitors，EDLC）因其高功率密度，长循环寿命和快速充放电能力而备受关注。然而，EDLC的稳定性和可靠性对于实际应用具有决定性的影响。为提升稳定性和延长寿命，深入了解性能衰减与失效机理至关重要。探讨了EDLC的失效标准以及性能衰减的监测和原位电化学表征方法。通过综述EDLC失效研究的新进展，聚焦于电极材料、电解液、电极-电解液界面及集流体等核心组件，旨在揭示不同体系中的失效现象和机理。最后，展望了高稳定性EDLC的发展方向和挑战，强调新材料开发与表征方法改进，为性能优化和应用拓展提供策略。

关键词: 失效机理, 失效标准, 炭电极, 有机电解液, 电极-电解液界面, 集流体

CLC Number:

TM 53

Guipei XU, Qian SUN, Jiewen LAI, Yifeng LU, Huifang DI, Hui HUANG, Zhenbing WANG. Research progress on failure mechanism of electrochemical double layer capacitors[J]. CIESC Journal, 2025, 76(3): 951-962.

徐桂培, 孙倩, 赖洁文, 卢毅锋, 邸会芳, 黄辉, 王振兵. 电化学双电层电容器失效机理的研究进展[J]. 化工学报, 2025, 76(3): 951-962.

Figures/Tables 7

Fig.1 Galvanostatic charge/discharge cycling and floating charge of organic (a) and aqueous (b) supercapacitors[16, 19]

Fig.2 Aging process and corresponding element flows of the internal components in EDLCs[43]

Fig.3 Schematic diagrams of the device for the gas chromatography-mass spectrometry cell[(a),(b)]; Total ion chromatograms (TICs) of the aged electrolyte at the positive (c) and negative (d) electrode[55]

Fig.4 Possible side-reaction mechanisms of EDLCs in each potential range of positive and negative electrodes[59, 62]

Fig.5 Failure mechanisms of EiPS-based EDLCs at high temperatures[64]

Fig.6 Possible decomposition reactions at the positive and/or negative electrode-electrolyte interface in AN-based EDLCs[55]

Table 1 Summary of key components and corresponding failure mechanisms in EDLC

失效部件	失效机理
炭电极	表面官能团氧化还原分解
	电极内吸附水发生氧化还原分解
	表面官能团和杂质与电解液作用发生副反应
电解液	溶剂发生水解、聚合等副反应
电解液	电解质离子发生水解、霍夫曼消除等副反应
集流体	副产物（如HF等）腐蚀集流体

References 75

1	Zhang C Y, Yang Y, Liu X, et al. Mobile energy storage technologies for boosting carbon neutrality[J]. The Innovation, 2023, 4(6): 100518.
2	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.
3	Salanne M, Rotenberg B, Naoi K, et al. Efficient storage mechanisms for building better supercapacitors[J]. Nature Energy, 2016, 1(6): 16070.
4	Ji H X, Zhao X, Qiao Z H, et al. Capacitance of carbon-based electrical double-layer capacitors[J]. Nature Communications, 2014, 5: 3317.
5	左飞龙, 陈照荣, 傅冠生, 等. 超级电容器用有机电解液的研究进展[J]. 电池, 2015, 45(2): 112-115.
	Zuo F L, Chen Z R, Fu G S, et al. Research progress in organic electrolytes for supercapacitor[J]. Battery Bimonthly, 2015, 45(2): 112-115.
6	Ruther R E, Sun C N, Holliday A, et al. Stable electrolyte for high voltage electrochemical double-layer capacitors[J]. Journal of the Electrochemical Society, 2016, 164(2): A277-A283.
7	Köps L, Kreth F A, Bothe A, et al. High voltage electrochemical capacitors operating at elevated temperature based on 1,1-dimethylpyrrolidinium tetrafluoroborate[J]. Energy Storage Materials, 2022, 44: 66-72.
8	Han J, Yoshimoto N, Todorov Y M, et al. Characteristics of the electric double-layer capacitors using organic electrolyte solutions containing different alkylammonium cations[J]. Electrochimica Acta, 2018, 281: 510-516.
9	Sun Q, Yi Z L, Fan Y F, et al. Whole landscape of the origin and evolution of gassing in supercapacitors at a high voltage[J]. ACS Applied Materials & Interfaces, 2023, 15(47): 54386-54396.
10	Liu S, Wei L, Wang H, et al. Review on reliability of supercapacitors in energy storage applications[J]. Applied Energy, 2020, 278: 115436.
11	Burke A. Ultracapacitors: why, how, and where is the technology[J]. Journal of Power Sources, 2000, 91(1): 37-50.
12	Simon P, Gogotsi Y. Materials for electrochemical capacitors[J]. Nature Materials, 2008, 7(11): 845-854.
13	Pal B, Yang S Y, Ramesh S, et al. Electrolyte selection for supercapacitive devices: a critical review[J]. Nanoscale Advances, 2019, 1(10): 3807-3835.
14	Zhao J Y, Burke A F. Review on supercapacitors: Technologies and performance evaluation[J]. Journal of Energy Chemistry, 2021, 59: 276-291.
15	Chaari R, Briat O, Delétage J Y, et al. How supercapacitors reach end of life criteria during calendar life and power cycling tests[J]. Microelectronics Reliability, 2011, 51(9/10/11): 1976-1979.
16	Weingarth D, Foelske-Schmitz A, Kötz R. Cycle versus voltage hold-Which is the better stability test for electrochemical double layer capacitors?[J]. Journal of Power Sources, 2013, 225: 84-88.
17	Rizoug N, Bartholomeus P, Le Moigne P. Study of the ageing process of a supercapacitor module using direct method of characterization[J]. IEEE Transactions on Energy Conversion, 2012, 27(2): 220-228.
18	Ratajczak P, Jurewicz K, Skowron P, et al. Effect of accelerated ageing on the performance of high voltage carbon/carbon electrochemical capacitors in salt aqueous electrolyte[J]. Electrochimica Acta, 2014, 130: 344-350.
19	Platek A, Piwek J, Fic K, et al. Ageing mechanisms in electrochemical capacitors with aqueous redox-active electrolytes[J]. Electrochimica Acta, 2019, 311: 211-220.
20	Hahn M, Würsig A, Gallay R, et al. Gas evolution in activated carbon/propylene carbonate based double-layer capacitors[J]. Electrochemistry Communications, 2005, 7(9): 925-930.
21	Bondue C J, Abd-El-Latif A A, Hegemann P, et al. Quantitative study for oxygen reduction and evolution in aprotic organic electrolytes at gas diffusion electrodes by DEMS[J]. Journal of the Electrochemical Society, 2015, 162(3): A479-A487.
22	Metzger M, Gasteiger H A. Diagnosing battery degradation via gas analysis[J]. Energy & Environmental Materials, 2022, 5(3): 688-692.
23	Kost R, Balducci A. Gas characterization- and mass spectrometry-tools for the analysis of aging in electrical double layer capacitors: state-of-the-art and future challenges[J]. ChemElectroChem, 2024, 11(18): e202400338.
24	Wang C, Frogley M D, Cinque G, et al. Deformation and failure mechanisms in graphene oxide paper using in situ nanomechanical tensile testing[J]. Carbon, 2013, 63: 471-477.
25	Prehal C, Weingarth D, Perre E, et al. Tracking the structural arrangement of ions in carbon supercapacitor nanopores using in situ small-angle X-ray scattering[J]. Energy & Environmental Science, 2015, 8(6): 1725-1735.
26	Kurzweil P, Chwistek M. Electrochemical stability of organic electrolytes in supercapacitors: spectroscopy and gas analysis of decomposition products[J]. Journal of Power Sources, 2008, 176(2): 555-567.
27	Manova D, Mändl S. In situ XRD measurements to explore phase formation in the near surface region[J]. Journal of Applied Physics, 2019, 126(20): 200901.
28	Liu L Y, Taberna P-L, Dunn B, et al. Future directions for electrochemical capacitors[J]. ACS Energy Letters, 2021, 6(12): 4311-4316.
29	Su X L, Ye J L, Zhu Y W. Advances in in-situ characterizations of electrode materials for better supercapacitors[J]. Journal of Energy Chemistry, 2021, 54: 242-253.
30	Kim J, Gerelt-Od B, Shin E, et al. State of health monitoring by gas generation patterns in commercial 18,650 lithium-ion batteries[J]. Journal of Electroanalytical Chemistry, 2022, 907: 115892.
31	Kim J, Kim E, Lee U, et al. Nondisruptive in situ Raman analysis for gas evolution in commercial supercapacitor cells[J]. Electrochimica Acta, 2016, 219: 447-452.
32	Wang Z F, Tang C, Sun Q, et al. Effect of N-doping-derived solvent adsorption on electrochemical double layer structure and performance of porous carbon[J]. Journal of Energy Chemistry, 2023, 80: 120-127.
33	Arruda T M, Heon M, Presser V, et al. In situ tracking of the nanoscale expansion of porous carbon electrodes[J]. Energy & Environmental Science, 2013, 6(1): 225-231.
34	Black J M, Feng G, Fulvio P F, et al. Strain-based in situ study of anion and cation insertion into porous carbon electrodes with different pore sizes[J]. Advanced Energy Materials, 2014, 4(3): 1300683.
35	Wang S, Xu H B, Hao T T, et al. In situ XRD and operando spectra-electrochemical investigation of tetragonal WO_3- _x nanowire networks for electrochromic supercapacitors[J]. NPG Asia Materials, 2021, 13(1): 51.
36	Camci M T, Ulgut B, Kocabas C, et al. In situ XPS reveals voltage driven asymmetric ion movement of an ionic liquid through the pores of a multilayer graphene electrode[J]. The Journal of Physical Chemistry C, 2018, 122(22): 11883-11889.
37	Tsai W Y, Taberna P L, Simon P. Electrochemical quartz crystal microbalance (EQCM) study of ion dynamics in nanoporous carbons[J]. Journal of the American Chemical Society, 2014, 136(24): 8722-8728.
38	Yao M H, Wu P, Cheng S, et al. Investigation into the energy storage behaviour of layered α-V₂O₅ as a pseudo-capacitive electrode using operando Raman spectroscopy and a quartz crystal microbalance[J]. Physical Chemistry Chemical Physics, 2017, 19(36): 24689-24695.
39	Escher I, Hahn M,. Ferrero G A, et al. A practical guide for using electrochemical dilatometry as operando tool in battery and supercapacitor research[J]. Energy Technology, 2022, 10(5): 2101120.
40	Kurzweil P, Schottenbauer J, Schell C. Past, present and future of electrochemical capacitors: pseudocapacitance, aging mechanisms and service life estimation[J]. Journal of Energy Storage, 2021, 35: 102311.
41	王其钰, 王朔, 周格, 等. 锂电池失效分析与研究进展[J]. 物理学报, 2018, 67(12): 279-290.
	Wang Q Y, Wang S, Zhou G, et al. Progress on the failure analysis of lithium battery[J]. Acta Physica Sinica, 2018, 67(12): 279-290.
42	Huang Y L, Zhao Y, Gong Q M, et al. Experimental and correlative analyses of the ageing mechanism of activated carbon based supercapacitor[J]. Electrochimica Acta, 2017, 228: 214-225.
43	Huang Y L, Weng M Y, Gong Q M, et al. Degeneration of key structural components resulting in ageing of supercapacitors and the related chemical ageing mechanism[J]. ACS Applied Materials & Interfaces, 2021, 13(33): 39379-39393.
44	Zhu M, Weber C J, Yang Y, et al. Chemical and electrochemical ageing of carbon materials used in supercapacitor electrodes[J]. Carbon, 2008, 46(14): 1829-1840.
45	Ruch P W, Cericola D, Foelske A, et al. A comparison of the aging of electrochemical double layer capacitors with acetonitrile and propylene carbonate-based electrolytes at elevated voltages[J]. Electrochimica Acta, 2010, 55(7): 2352-2357.
46	Bittner A M, Zhu M, Yang Y, et al. Ageing of electrochemical double layer capacitors[J]. Journal of Power Sources, 2012, 203: 262-273.
47	Beguin F, Presser V, Balducci A, et al. Carbons and electrolytes for advanced supercapacitors[J]. Advanced Materials, 2014, 26(14): 2219-2251.
48	Yan R Y, Antonietti M, Oschatz M. Toward the experimental understanding of the energy storage mechanism and ion dynamics in ionic liquid based supercapacitors[J]. Advanced Energy Materials, 2018, 8(18): 1800026.
49	Chmiola J, Yushin G, Dash R, et al. Effect of pore size and surface area of carbide derived carbons on specific capacitance[J]. Journal of Power Sources, 2006, 158(1): 765-772.
50	Ratajczak P, Suss M E, Kaasik F, et al. Carbon electrodes for capacitive technologies[J]. Energy Storage Materials, 2019, 16: 126-145.
51	Barbieri O, Hahn M, Herzog A, et al. Capacitance limits of high surface area activated carbons for double layer capacitors[J]. Carbon, 2005, 43(6): 1303-1310.
52	Deschamps M, Gilbert E, Azais P, et al. Exploring electrolyte organization in supercapacitor electrodes with solid-state NMR[J]. Nature Materials, 2013, 12(4): 351-358.
53	Lin R Y, Taberna P-L, Fantini S, et al. Capacitive energy storage from -50 to 100℃ using an ionic liquid electrolyte[J]. The Journal of Physical Chemistry Letters, 2011, 2(19): 2396-2401.
54	Ruch P W, Cericola D, Foelske-Schmitz A, et al. Aging of electrochemical double layer capacitors with acetonitrile-based electrolyte at elevated voltages[J]. Electrochimica Acta, 2010, 55(15): 4412-4420.
55	Kreth F A, Hess L H, Balducci A. In-operando GC-MS: a new tool for the understanding of degradation processes occurring in electrochemical capacitors[J]. Energy Storage Materials, 2023, 56: 192-204.
56	Kötz R, Hahn M, Ruch P, et al. Comparison of pressure evolution in supercapacitor devices using different aprotic solvents[J]. Electrochemistry Communications, 2008, 10(3): 359-362.
57	Azaïs P, Duclaux L, Florian P, et al. Causes of supercapacitors ageing in organic electrolyte[J]. Journal of Power Sources, 2007, 171(2): 1046-1053.
58	Hahn M, Kötz R, Gallay R, et al. Pressure evolution in propylene carbonate based electrochemical double layer capacitors[J]. Electrochimica Acta, 2006, 52(4): 1709-1712.
59	Ishimoto S, Asakawa Y, Shinya M, et al. Degradation responses of activated-carbon-based EDLCs for higher voltage operation and their factors[J]. Journal of the Electrochemical Society, 2009, 156(7): A563-A571.
60	Munteshari O, Borenstein A, DeBlock R H, et al. In operando calorimetric measurements for activated carbon electrodes in ionic liquid electrolytes under large potential windows[J]. ChemSusChem, 2020, 13(5): 1013-1026.
61	Hess L H, Bothe A, Balducci A. Design and use of a novel in situ simultaneous thermal analysis cell for an accurate "real time" monitoring of the heat and weight changes occurring in electrochemical capacitors[J]. Energy Technology, 2021, 9(9): 2100329.
62	Liu C F, Liu Y C, Yi T, et al. Carbon materials for high-voltage supercapacitors[J]. Carbon, 2019, 145: 529-548.
63	Chiba K, Ueda T, Yamaguchi Y, et al. Electrolyte systems for high withstand voltage and durability (Ⅰ). Linear sulfones for electric double-layer capacitors[J]. Journal of the Electrochemical Society, 2011, 158(8): A872-A882.
64	Köps L, Kreth F A, Leistenschneider D, et al. Improving the stability of supercapacitors at high voltages and high temperatures by the implementation of ethyl isopropyl sulfone as electrolyte solvent[J]. Advanced Energy Materials, 2023, 13(5): 2203821.
65	Pourhosseini S E M, Bothe A, Balducci A, et al. Strategy to assess the carbon electrode modifications associated with the high voltage ageing of electrochemical capacitors in organic electrolyte[J]. Energy Storage Materials, 2021, 38: 17-29.
66	He M L, Fic K, Fŗckowiak E, et al. Ageing phenomena in high-voltage aqueous supercapacitors investigated by in situ gas analysis[J]. Energy & Environmental Science, 2016, 9(2): 623-633.
67	Lamiel C, Hussain I, Ma X X, et al. Properties, functions, and challenges: current collectors[J]. Materials Today Chemistry, 2022, 26: 101152.
68	Krämer E, Schedlbauer T, Hoffmann B, et al. Mechanism of anodic dissolution of the aluminum current collector in 1 M LiTFSI EC:DEC 3:7 in rechargeable lithium batteries[J]. Journal of the Electrochemical Society, 2012, 160(2): A356-A360.
69	Holleman A F, Wiberg N, Wiberg E. Lehrbuch der Anorganischen Chemie[M]. 102nd ed. Berlin, Boston: De Gruyter, 2008: 1156.
70	Wu H, Song Z Y, Wang X X, et al. N,N-dimethyl fluorosulfonamide for suppressed aluminum corrosion in lithium bis(trifluoromethanesulfonyl)imide-based electrolytes[J]. Nano Research, 2023, 16(6): 8269-8280.
71	Heckmann A, Krott M, Streipert B, et al. Suppression of aluminum current collector dissolution by protective ceramic coatings for better high-voltage battery performance[J]. ChemPhysChem, 2017, 18(1): 156-163.
72	Krummacher J, Balducci A. Al(TFSI)₃ as a conducting salt for high-voltage electrochemical double-layer capacitors[J]. Chemistry of Materials, 2018, 30(14): 4857-4863.
73	Yoon E, Lee J, Byun S, et al. Passivation failure of Al current collector in LiPF₆-based electrolytes for lithium-ion batteries[J]. Advanced Functional Materials, 2022, 32(22): 2200026.
74	Chandra Sekhar B, Hachicha R, Maffre M, et al. Evaluation of the properties of an electrolyte based on formamide and LiTFSI for electrochemical capacitors[J]. Journal of the Electrochemical Society, 2020, 167(11): 110508.
75	Meister P, Qi X, Kloepsch R, et al. Anodic behavior of the aluminum current collector in imide-based electrolytes: influence of solvent, operating temperature, and native oxide-layer thickness[J]. ChemSusChem, 2017, 10(4): 804-814.

[1]	Yunhao LI, Juncheng JIANG, Yuan YU, Zhirong WANG, Qingwu ZHANG. Coupling effects of perforation and heat radiation on failure mechanism of fixed-roof steel tank [J]. CIESC Journal, 2021, 72(8): 4433-4443.
[2]	BIAN Weibai, PAN Jianming. Research progress on electro-sorption technology and fabrication of adsorptive electrode materials [J]. CIESC Journal, 2021, 72(1): 304-319.
[3]	ZHANG Jianwen, SU Guoqing, JIANG Aiguo. Corrosion failure mechanism of return pipeline elbow of regeneration tower in LPG desulfurization unit [J]. CIESC Journal, 2018, 69(8): 3537-3547.
[4]	SHEN Kejun，PEI Junfeng，HE Chao，HUANG Xianru. Reciprocating pump hydraulic end failure mechanism based on blind source separation [J]. Chemical Industry and Engineering Progree, 2014, 33(03): 611-616.
[5]	WANG Xiaojuan, WU Beilei, MA Chun'an. Electrochemical oxidation characteristics of zinc O,O,O’,O’-tetrabutyl bis(phosphorodithioate)on glassy carbon electrode [J]. CIESC Journal, 2013, 64(7): 2550-2555.