Abstract
Supercapacitor technology is one of the most flourishing renewable and sustainable energy supports that satisfactorily addresses the sky-rising demands of nonstop power supply. However, corresponding currently available supercapacitors/ ultracapacitors primarily lack adequate energy densities besides high fabrication costs, adaptability, and other technical problems, such as high self-discharge rates, resulting in short-term energy storage, that limit their boundless commercialization. Various strategies have been adopted for upgrading these devices’ energy performances that include the essential need for extended potential window which can be reasonably accomplished through appropriate choice of electrolytes, along with judicious electrode material designing. Rightly, electrolytes have turned out to be an imperative “performance-dictating” constituent in the electrochemical energy storage systems. The electrolytes are also crucial for ensuring device thermal stability, internal resistances, controlling self-discharges, durability, etc. They have been traditionally used in liquid forms such as aqueous, nonaqueous/organic, ionic liquids for high-performing supercapacitors. This chapter provides an outline of the latest advancements of popular liquid-based electrolytes employed in various supercapacitors. The basic ideas for scheming and optimizing electrolyte characteristics considering their production cost, availability, and environmental benignity have also been highlighted. Conclusively, some propositions have been put forward that might be handful in overcoming the current challenges faced without compromising with the existing benefits.
This is a preview of subscription content, log in via an institution to check access.
References
T. Abdallah, D. Lemordant, B. Claude-Montigny, Are room temperature ionic liquids able to improve the safety of supercapacitors organic electrolytes without degrading the performances? J. Power Sources 201, 353–359 (2012). https://doi.org/10.1016/j.jpowsour.2011.10.115
B. Akinwolemiwa, C. Peng, G.Z. Chen, Redox electrolytes in supercapacitors. J. Electrochem. Soc. 162, A5054 (2015). https://doi.org/10.1149/2.0111505jes
D. Aradilla, P. Gentile, V. Ruiz, et al., SiNWs-based electrochemical double layer micro-supercapacitors with wide voltage window (4 V) and long cycling stability using a protic ionic liquid electrolyte. Adv. Nat. Sci. Nanosci. Nanotechnol. 6, 015004 (2015). https://doi.org/10.1088/2043-6262/6/1/015004
M. Arulepp, L. Permann, J. Leis, et al., Influence of the solvent properties on the characteristics of a double layer capacitor. J. Power Sources 133, 320–328 (2004). https://doi.org/10.1016/j.jpowsour.2004.03.026
T.E. Balaji, H.T. Das, T. Maiyalagan, Recent trends in bimetallic oxides and their composites as electrode materials for supercapacitor applications. ChemElectroChem 8, 1723–1746 (2021). https://doi.org/10.1002/CELC.202100098
W. Bo, C. Zhaohui, L. Gang, et al., Exploring electrolyte preference of vanadium nitride supercapacitor electrodes. Mater. Res. Bull. 76, 37–40 (2016). https://doi.org/10.1016/j.materresbull.2015.12.006
A. Brandt, P. Isken, A. Lex-Balducci, et al., Adiponitrile-based electrochemical double layer capacitor. J. Power Sources 204, 213–219 (2012). https://doi.org/10.1016/j.jpowsour.2011.12.025
A. Brandt, S. Pohlmann, A. Varzi, et al., Ionic liquids in supercapacitors. MRS Bull. 38, 554–559 (2013). https://doi.org/10.1557/mrs.2013.151
J.-K. Chang, M.-T. Lee, C.-W. Cheng, et al., Evaluation of ionic liquid electrolytes for use in manganese oxide supercapacitors. Electrochem. Solid State Lett. 12, A19–A22 (2009). https://doi.org/10.1149/1.3013028
L. Chen, H. Bai, Z. Huang, et al., Mechanism investigation and suppression of self-discharge in active electrolyte enhanced supercapacitors. Energy Environ. Sci. 7, 1750–1759 (2014). https://doi.org/10.1039/C4EE00002A
Y. Cui, L. Cheng, C. Wen, et al., Capacitive behavior of chestnut shell-based porous carbon electrode in ionic liquid electrolytes. Colloids Surf. A Physicochem. Eng. Asp. 508, 173–177 (2016). https://doi.org/10.1016/j.colsurfa.2016.08.044
H.T. Das, K. Mahendraprabhu, T. Maiyalagan, et al., Performance of solid-state hybrid energy-storage device using reduced graphene-oxide anchored sol-gel derived Ni/NiO nanocomposite. Sci. Rep. 7, 1–14 (2017). https://doi.org/10.1038/s41598-017-15444-z
R. Edurne, G. Eider, M. Roman, The decisive role of electrolyte concentration in the performance of aqueous chloride-based carbon/carbon supercapacitors with extended voltage window. Electrochim. Acta 221, 177–183 (2016). https://doi.org/10.1016/j.electacta.2016.10.141
O. Ellabban, H. Abu-Rub, F. Blaabjerg, Renewable energy resources: Status, future prospects, and their enabling technology. Renew. Sust. Energ. Rev. 39, 748–764 (2014). https://doi.org/10.1016/j.rser.2014.07.113
K. Fic, G. Lota, M. Meller, et al., Novel insight into neutral medium as electrolyte for high-voltage supercapacitors. Energy Environ. Sci. 5, 5842–5850 (2012). https://doi.org/10.1039/C1EE02262H
E. Frackowiak, K. Fic, M. Meller, et al., Electrochemistry serving people and nature: High-energy ecocapacitors based on redox-active electrolytes. Chem. Sustain. Chem. 5, 1181–1185 (2012). https://doi.org/10.1002/cssc.201200227
E. Frackowiak, M. Meller, J. Menzel, et al., Redox-active electrolyte for supercapacitor application. Faraday Discuss. 172, 179–198 (2014). https://doi.org/10.1039/C4FD00052H
H. Gao, A. Virya, Lian, et al., Monovalent silicotungstate salts as electrolytes for electrochemical supercapacitors. Electrochim. Acta 138, 240–246 (2014). https://doi.org/10.1016/j.electacta.2014.06.127
H.L. George, J. Erik, Electrochemical studies of acetonitrile based supercapacitor electrolytes containing alkali and alkaline earth metal cations. Electrochim. Acta 150, 173–187 (2014). https://doi.org/10.1016/j.electacta.2014.10.112
B. Gorska, E. Frackowiak, F. Beguin, Redox active electrolytes in carbon/carbon electrochemical capacitors. Curr. Opin. Electrochem. 9, 95–105 (2018). https://doi.org/10.1016/j.coelec.2018.05.006
Q. Gou, S. Zhao, J. Wang, et al., Recent advances on boosting the cell voltage of aqueous supercapacitors. Nano-Micro. Lett. 12, 98 (2020). https://doi.org/10.1007/s40820-020-00430-4
K. Heisi, J. Alar, L. Enn, Electrochemical characteristics of carbide-derived carbon mid 1 -Ethyl-3-methylimidazolium Tetrafluoroborate supercapacitor cells. J. Electrochem. Soc. 157, A272 (2010). https://doi.org/10.1149/1.3274208
P.-L. Huang, X.-F. Luo, Y.-Y. Peng, et al., Ionic liquid electrolytes with various constituent ions for graphene-based supercapacitors. Electrochim. Acta 161, 371–377 (2015). https://doi.org/10.1016/j.electacta.2015.02.115
C.M. Ionica-Bousquet, W.J. Casteel, R.M. Pearlstein, et al., Polyfluorinated boron cluster-[B12F11H]2−-based electrolytes for supercapacitors: Overcharge protection. Electrochem. Commun. 12, 636–639 (2010). https://doi.org/10.1016/j.elecom.2010.02.018
D. Jiang, J. Wu, Unusual effects of solvent polarity on capacitance for organic electrolytes in a nanoporous electrode. Nanoscale 6, 5545–5550 (2014). https://doi.org/10.1039/C4NR00046C
D. Jiang, Z. Jin, D. Henderson, et al., Solvent effect on the pore-size dependence of an organic electrolyte supercapacitor. J. Phys. Chem. Lett. 3, 1727–1731 (2012). https://doi.org/10.1021/jz3004624
R.S. Kalubarme, H.S. Jadhav, C.-J. Park, Electrochemical characteristics of two-dimensional nano-structured MnO2 for symmetric supercapacitor. Electrochim. Acta 87, 457–465 (2013). https://doi.org/10.1016/j.electacta.2012.09.081
M.N. Khrizanforov, V.V. Grinenko, S.O. Strekalova, et al., Phosphonium-based ionic liquids as electrolyte for supercapacitors. Phosphorus Sulfur Silicon Relat. Elem. 194, 388–390 (2019). https://doi.org/10.1080/10426507.2018.1564307
P. Kumar, S. Yashonath, et al., Ionic conductivity in aqueous electrolyte solutions: Insights from computer simulations. J. Mol. Liq. 277, 506–515 (2019). https://doi.org/10.1016/j.molliq.2018.12.090
E.H. Lahrar, I. Deroche, C.M. Ghimbeu, et al., Simulations of ionic liquids confined in surface-functionalized nanoporous carbons: Implications for energy storage. ACS Appl. Nano Mater. 4, 4007–4015 (2021). https://doi.org/10.1021/acsanm.1c00342
P. Lannelongue, R. Bouchal, E. Mourad, et al., Water-in-salt for supercapacitors: A compromise between voltage, power density, energy density and stability. J. Electrochem. Soc. 165, A657–A663 (2018). https://doi.org/10.1149/2.0951803jes
W.S.V. Lee, T. Xiong, G.C. Loh, et al., Optimizing electrolyte physiochemical properties toward 2.8 V aqueous supercapacitor. ACS Appl. Energy Mater. 1, 3070–3076 (2018). https://doi.org/10.1021/acsaem.8b00751
D. Leistenschneider, L.H. He, A. Balducci, et al., Solid-state transformation of aqueous to organic electrolyte-enhancing the operating voltage window of in situ electrolyte supercapacitors. Sustain. Energy Fuels 4, 2438–2444 (2020). https://doi.org/10.1039/D0SE00180E
Q. Li, K. Li, C. Sun, et al., An investigation of Cu2+ and Fe2+ ions as active materials for electrochemical redox supercapacitors. J. Electroanal. Chem. 611, 43–50 (2007). https://doi.org/10.1016/j.jelechem.2007.07.022
H. Li, Y. Tao, X. Zheng, et al., Ultra-thick graphene bulk supercapacitor electrodes for compact energy storage. Energy Environ. Sci. 9, 3135–3142 (2016). https://doi.org/10.1039/C6EE00941G
R. Lin, P.L. Taberna, J. Chmiola, et al., Microelectrode study of pore size, ion size, and solvent effects on the charge/discharge behavior of microporous carbons for electrical double-layer capacitors. J. Electrochem. Soc. 156, A7 (2009). https://doi.org/10.1149/1.3002376
G. Lota, E. Frackowiak, et al., Striking capacitance of carbon/iodide interface. Electrochem. Commun. 11, 87–90 (2009). https://doi.org/10.1016/2Fj.elecom.2008.10.026
K. Mahankali, N.K. Thangavel, Y. Ding, et al., Interfacial behavior of water-in-salt electrolytes at porous electrodes and its effect on supercapacitor performance. Electrochim. Acta 326, 134989 (2019). https://doi.org/10.1016/j.electacta.2019.134989
L.Q. Mai, A. Minhas-Khan, X. Tian, et al., Synergistic interaction between redox-active electrolyte and binder-free functionalized carbon for ultrahigh supercapacitor performance. Nat. Commun. 4, 2923–2927 (2013). https://doi.org/10.1038/ncomms3923
D. Majumdar, Recent progress in copper sulfide based nanomaterials for high energy supercapacitor applications. J. Electroanal. Chem. 880, 114825 (2021a). https://doi.org/10.1016/j.jelechem.2020.114825
D. Majumdar, Aqueous electrolytes for flexible supercapacitors, in Flexible supercapacitor nanoarchitectonics, ed. by M. I. A. Inamuddin, R. Boddula, (Wiley, 2021b). https://doi.org/10.1002/9781119711469
D. Majumdar, M. Mandal, S.K. Bhattacharya, Journey from supercapacitors to supercapatteries: Recent advancements in electrochemical energy storage systems. Emergent mater. 3, 347–367 (2020). https://doi.org/10.1007/s42247-020-00090-5
J.K. McDonough, A.I. Frolov, V. Presser, et al., Influence of the structure of carbon onions on their electrochemical performance in supercapacitor electrodes. Carbon 50, 3298–3309 (2012). https://doi.org/10.1016/j.carbon.2011.12.022
M.D. Merrill, E. Montalvo, P.G. Campbell, et al., Optimizing supercapacitor electrode density: Achieving the energy of organic electrolytes with the power of aqueous electrolytes. RSC Adv. 4, 42942–42946 (2014). https://doi.org/10.1039/C4RA08114E
C. Ming, F. Guang, Q. Rui, Water-in-salt electrolytes: An interfacial perspective. Curr. Opin. Colloid Interface Sci. 47, 99–110 (2020). https://doi.org/10.1016/j.cocis.2019.12.011
P. Navalpotro, J. Palma, M. Anderson, et al., High performance hybrid supercapacitors by using Para-benzoquinone ionic liquid redox electrolyte. J. Power Sources 306, 711–717 (2016). https://doi.org/10.1016/j.jpowsour.2015.12.103.Ji
Q.D. Nguyen, J. Patra, C.T. Hsieh, et al., Supercapacitive properties of micropore- and mesopore-rich activated carbon in ionic-liquid electrolytes with various constituent ions. ChemSusChem 12, 449–456 (2019). https://doi.org/10.1002/cssc.201802489
A. Orita, K. Kamijima, M. Yoshida, Allyl-functionalized ionic liquids as electrolytes for electric double-layer capacitors. J. Power Sources 195, 7471–7479 (2010). https://doi.org/10.1016/j.jpowsour.2010.05.066
B. Pal, S. Yang, S. Ramesh, et al., Electrolyte selection for supercapacitive devices: A critical review. Nanoscale Adv. 1, 3807–3835 (2019). https://doi.org/10.1039/C9NA00374F
S. Pan, J. Deng, G. Guan, et al., A redoxactive gel electrolyte for fiber-shaped supercapacitor with high area specific capacitance. J. Mater. Chem. A 3, 6286–6290 (2015). https://doi.org/10.1039/C5TA00007F
M. Pang, S. Jiang, J. Zhao, et al., Water-in-salt electrolyte enhanced high voltage aqueous supercapacitor with carbon electrodes derived from biomass waste-ground grain hulls. RSC Adv. 10, 35545–35556 (2020). https://doi.org/10.1039/d0ra07448a
E. Perricone, M. Chamas, J.-C. Lepretre, et al., Safe and performant electrolytes for supercapacitor, investigation of esters/carbonate mixtures. J. Power Sources 239, 217–224 (2013). https://doi.org/10.1016/j.jpowsour.2013.03.123
F. Robert, C. Dario, K. Rudiger, et al., Novel electrolytes for electrochemical double layer capacitors based on 1,1,1,3,3,3-hexafluoropropan-2-ol. Electrochim. Acta 62, 372–380 (2012). https://doi.org/10.1016/j.electacta.2011.12.050
D. Rochefort, A.L. Pont, Pseudocapacitive behavior of RuO2 in a proton exchange ionic liquid. Electrochem. Commun. 8, 1539–1543 (2006). https://doi.org/10.1016/j.elecom.2006.06.032
S. Roldan, M. Granda, R. Menendez, et al., Mechanisms of energy storage in carbon-based supercapacitors modified with a quinoid redox-active electrolyte capacitance. J. Phys. Chem. C 115, 17606–17611 (2011). https://doi.org/10.1021/jp205100v
Y. Shao, M.F. El-Kady, S.J. Li, et al., Design and mechanisms of asymmetric supercapacitors. Chem. Rev. 118, 9233–9280 (2018). https://doi.org/10.1021/acs.chemrev.8b00252
L. Su, L. Gong, H. Lu, et al., Enhanced low-temperature capacitance of MnO2 nanorods in a redox-active electrolyte. J. Power Sources 248, 212–217 (2014). https://doi.org/10.1016/j.jpowsour.2013.09.047
J. Suarez-Guevara, V. Ruiz, P. Gomez-Romero, Hybrid energy storage: High voltage aqueous supercapacitors based on activated carbon–phosphotungstate hybrid materials. J. Mater. Chem. A 2, 1014–1021 (2014). https://doi.org/10.1039/C3TA14455K
M.M. Sundaram, D. Appadoo, Traditional salt-in-water electrolyte vs. water-in- salt electrolyte with binary metal oxide for symmetric supercapacitors: Capacitive vs. faradaic. Dalton Trans. 49, 11743–11755 (2020). https://doi.org/10.1039/d0dt01871f
Y. Tian, R. Xue, X. Zhou, et al., Double layer capacitor based on active carbon and its improved capacitive properties using redox additive electrolyte of anthraquinonedisulphonate. Electrochim. Acta 152, 135–139 (2015). https://doi.org/10.1016/j.electacta.2014.11.120
L. Timperman, H. Galiano, D. Lemordant, et al., Phosphonium-based protic ionic liquid as electrolyte for carbon-based supercapacitors. Electrochem. Commun. 13, 1112–1115 (2011). https://doi.org/10.1016/j.elecom.2011.07.010
Q.M. Tu, L.Q. Fan, F. Pan, et al., Ionic liquid for flexible supercapacitors. Electrochim. Acta 268, 562–568 (2018). https://doi.org/10.1016/j.electacta.2018.02.008
G. Wang, R. Liang, L. Liu, et al., Improving the specific capacitance of carbon nanotubes-based supercapacitors by combing introducing funcitional groups on carbon nanotubes with using redox-active electrolyte. Electrochim. Acta 115, 183–188 (2014). https://doi.org/10.1016/j.electacta.2013.10.165
J. Wang, J. Wu, G. Lu, et al., Molecular dynamics study of the transport properties and local structures of molten alkali metal chlorides. Part III. Four binary systems LiCl-RbCl, LiCl-CsCl. NaCl-RbCl and NaCl-CsCl. J. Mol. Liq. 238, 236–247 (2017). https://doi.org/10.1016/j.molliq.2017.03.103
J. Yi, Z. Huo, A.M. Asiri, et al., Development and application of electrolytes in supercapacitors. Prog. Chem. 30, 1624–1633 (2018). https://doi.org/10.7536/PC180314
L. Yu, G.Z. Chen, Ionic liquid-based electrolytes for supercapacitor and supercapattery. Front. Chem. 7, 272–287 (2019). https://doi.org/10.3389/fchem.2019.00272
X. Yu, D. Ruan, C. Wu, et al., Spiro-(1,1′)-bipyrrolidinium tetrafluoroborate salt as high voltage electrolyte for electric double layer capacitors. J. Power Sources 265, 309–316 (2014). https://doi.org/10.1016/j.jpowsour.2014.04.144
C. Zhan, M.R. Ceron, S.A. Hawks, et al., Specific ion effects at graphitic interfaces. Nat. Commun. 10, 4858 (2019). https://doi.org/10.1038/s41467-019-12854-7
C. Zhong, Y. Deng, W. Hu, et al., A review of electrolyte materials and compositions for electrochemical supercapacitors. Chem. Soc. Rev. 44, 7484–7539 (2015). https://doi.org/10.1039/C5CS00303B
L. Zifeng, P.-L. Taberna, P. Simon, Graphene-based supercapacitors using eutectic ionic liquid mixture electrolyte. Electrochim. Acta 206, 446–451 (2016). https://doi.org/10.1016/j.electacta.2015.12.097
Acknowledgments
DM acknowledges Chandernagore College, Chandannagar, Hooghly, West Bengal, Pin-712136, India, for providing permission to do honorary research. HTD acknowledges RUSA, Utkal University, Bhubaneswar, for postdoctoral fellow funding.
Conflicts of Interest
The authors declare no conflict of interest.
Funding Assistance
This research received no funding assistance from any sources.
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Section Editor information
Rights and permissions
Copyright information
© 2022 Springer Nature Singapore Pte Ltd.
About this entry
Cite this entry
Majumdar, D., Das, H.T. (2022). Liquid Electrolytes for Supercapacitors. In: Gupta, R. (eds) Handbook of Energy Materials. Springer, Singapore. https://doi.org/10.1007/978-981-16-4480-1_22-1
Download citation
DOI: https://doi.org/10.1007/978-981-16-4480-1_22-1
Received:
Accepted:
Published:
Publisher Name: Springer, Singapore
Print ISBN: 978-981-16-4480-1
Online ISBN: 978-981-16-4480-1
eBook Packages: Springer Reference Chemistry and Mat. ScienceReference Module Physical and Materials ScienceReference Module Chemistry, Materials and Physics