MINI REVIEW

published: 03 June 2020

doi: 10.3389/fchem.2020.00413

A Review of Redox Electrolytes for

Supercapacitors
Le Zhang 1 , Shuhua Yang 1*, Jie Chang 2*, Degang Zhao 1 , Jieqiang Wang 1 , Chao Yang 3 and
Bingqiang Cao 1,3*
1
Materials Center for Energy and Photoelectrochemical Conversion, School of Material Science and Engineering, University
of Jinan, Jinan, China, 2 Key Laboratory of Micro-Nano Powder and Advanced Energy Material of Anhui Higher Education
Institutes, Chizhou University, Chizhou, China, 3 School of Physics and Physical Engineering, Qufu Normal University, Qufu,
China

Supercapacitors (SCs) have attracted widespread attention due to their short

charging/discharging time, long cycle life, and good temperature characteristics.
Electrolytes have been considered as a key factor affecting the performance of SCs.
They largely determine the energy density based on their decomposition voltage and the
power density from their ionic conductivity. In recent years, redox electrolytes obtained
a growing interest due to an additional redox activity from electrolytes, which offers an
increased charge storage capacity in SCs. This article summarizes the latest progress
Edited by:
Kwan San Hui, in the research of redox electrolytes, and focuses on their properties, mechanisms,
University of East Anglia, and applications based on different solvent types available. It also proposes potential
United Kingdom
solutions for how to effectively increase the energy density of the SCs while maintaining
Reviewed by:
Dmitry Medvedev,
their high power and long life.
Institute of High Temperature
Keywords: ionic conductivity, energy density, power density, redox electrolyte, supercapacitor
Electrochemistry (RAS), Russia
Le-Qing Fan,
Huaqiao University, China
INTRODUCTION
*Correspondence:
Shuhua Yang
Supercapacitors (SCs) are a new type of energy storage equipment filling the gap between secondary
[email protected]
Jie Chang
batteries and traditional capacitors (Hui et al., 2019; Poonam et al., 2019; Zhi-yu et al., 2019;
[email protected] Alipoori et al., 2020; Cheng et al., 2020; Iqbal et al., 2020; Li and Liang, 2020; Mohd Abdah et al.,
Bingqiang Cao 2020; Panda et al., 2020; Yi et al., 2020). SCs are believed to be one of the most promising candidates
[email protected] due to their fast charging/discharging capability, long cycle life, high power density, and high
safety (Zhang W. et al., 2017; Zhang et al., 2018; Afif et al., 2019). In the course of decades of
Specialty section: their development, the research on SCs has mainly focused on the preparation and modification
This article was submitted to of electrode materials to improve capacity (Zhao and Zheng, 2015). As an important part of SCs,
Electrochemistry,
electrolytes provide ionic conductivity and promote the charge compensation of electrodes (Wang
a section of the journal
Y. et al., 2016), so the performance of the SCs is determined by the electrolyte together with the
Frontiers in Chemistry
electrode material. The electrolyte has two key parameters: (1) Electrochemical stability window.
Received: 01 March 2020
If the electrode material doesn’t undergo any decomposition reaction within the voltage range
Accepted: 20 April 2020
of the SCs, then the output voltage of the device largely depends on the decomposition voltage
Published: 03 June 2020
of the electrolyte (Schütter et al., 2016). (2) Ionic conductivity. It affects the dynamic process and
Citation:
determines the rate capability of the SCs. It is related to the number of carriers, the ionic charge, and
Zhang L, Yang S, Chang J, Zhao D,
Wang J, Yang C and Cao B (2020) A
carrier mobility. The SCs electrolytes mainly have the following types: aqueous electrolytes, organic
Review of Redox Electrolytes for electrolytes, ionic liquid electrolytes, all solid electrolytes, gel electrolytes, and redox electrolytes
Supercapacitors. Front. Chem. 8:413. (Panda et al., 2020). Several reviews concerning electrolytes for SCs have been published previously
doi: 10.3389/fchem.2020.00413 (Zhao and Zheng, 2015; Zhong et al., 2015; Pal et al., 2019; Li et al., 2020). However, none of

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Zhang et al. Redox Electrolytes for Supercapacitors

the previous reviews concentrated on the dependence of to form a PPD-KOH electrolyte. As expected, the specific
properties, mechanisms, and applications of redox electrolytes on capacitance of the carbon sample in the PPD-KOH electrolyte
the different solvent types available. was larger (501.4 F g−1 at 3 A g−1 ) than that of SCs using an
Redox electrolytes are a specific type of electrolyte, in which electrolyte without PPD (119.2 F g−1 at 3 A g−1 ). Fic et al. (2015)
redox active species were added. They can greatly increase the demonstrated a new capacitor concept in which the positive
electrochemical performance of SCs for two reasons: (1) The electrode works in a KI solution and the negative electrode works
electrolyte additive is an active part of the SCs in redox reactions in a KOH electrolyte. Because of the redox reactions of I− /I2 , the
during charge and discharge processes (Sankar and Selvan, 2015; capacitance and energy density of the SCs is improved.
Sun et al., 2015b; Fan et al., 2016; Wang C. et al., 2016). (2) For neutral electrolytes, K3 Fe(CN)6 (Lee et al., 2016a), KI
The redox reactions in the electrolyte are conducive to electron (Singh and Chandra, 2016) and other additives with redox
transfer between the electrode material and the redox species properties (Chun et al., 2015) are usually added. Chun et al.
in the electrolyte (Dai et al., 2016; Vlad et al., 2016; Gao et al., (2015) found that a high energy density of about 14 Wh kg−1
2017; Mourad et al., 2017; Xiong et al., 2017). This review was obtained under methyl viologen (MV)/bromide electrolytes
mainly summarizes the latest research results of various redox due to the redox reactions of Br− /Br− 2+
3 and MV /MV . The
+

electrolytes based on aqueous, organic, ionic, and gel solvents. stability was improved by substituting heptyl viologen (HV) for
MV and did not degrade after 20,000 cycles. It is believed that this
electrolyte system will gain a foothold in future advanced energy
REDOX MEDIATED AQUEOUS storage applications.
ELECTROLYTES Despite making considerable progress, the low decomposition
voltage of water (1.23 V) leads to a poor energy density of SCs
Aqueous electrolytes can be divided into three types: (Yi et al., 2020). It is also reported that the cycle performance of
acidic, alkaline, and neutral solutions. As a commonly used SCs will deteriorate after adding redox additives to the aqueous
electrolyte, sulfuric acid aqueous solution not only has high electrolytes (Chodankar et al., 2016; Singh and Chandra, 2016).
ion conductivity/concentration but also low equivalent series This is mainly because a strong redox reaction occurs at the
resistance. Therefore, adding redox additives to sulfuric acid electrode/electrolyte interfaces, which will affect the electroactive
aqueous solution is a good way to optimize the electrolyte and site to a certain extent (Chodankar et al., 2016).
improve the performance of SCs. Some typical redox additives
contain KI (Zhang Y. et al., 2017; Gao et al., 2018), Na2 MoO4
(Xu et al., 2017a), Ce2 (SO4 )3 (Díaz et al., 2015), Fe3+ /Fe2+ (Ren REDOX MEDIATED ORGANIC
et al., 2017), viologen substances (Sathyamoorthi et al., 2016), ELECTROLYTES
1,4-dihydroxyanthraquinone (Xu et al., 2017b), hydroquinone
(HQ) (Pham et al., 2015; Chen and Lin, 2019), and so on. In order to increase the energy density, an organic electrolyte
Generally, the energy density based on multiple redox with a wide electrochemical stability window (around 3 V) is a
additives is higher than that based on a single redox additive good choice (Zhao and Zheng, 2015). The organic system consists
in aqueous electrolytes (Lee et al., 2016b; Teng et al., 2016). of organic solvents and conductive salts. Propylene carbonate
When using mixed electrolytes, their ratio is a key factor (PC) (Li et al., 2015; Salunkhe et al., 2016) and acetonitrile (AC)
for the performance of SCs. Xu et al. (2017a) adjusted the (Dall’Agnese et al., 2016; Jäckel et al., 2016; Singh and Chandra,
overlapping redox voltage windows by the ratio of Na2 MoO4 2016; Yang et al., 2017) are the most commonly used solvents in
to KI. The optimal system (Na2 MoO4 : KI = 1:1) shows SCs. Tetraethyl ammonium tetrafluoroborate (TEABF4 ) (Li et al.,
higher capacitance (the capacitance increased by 17.4 times) 2015; Jäckel et al., 2016; Salunkhe et al., 2016; Singh and Chandra,
and better rate performance than other systems (Na2 MoO4 : 2016; Yang et al., 2017) and LiPF6 (Xie L. et al., 2016) are the most
KI 6= 1:1) due to a synergistic effect between Na2 MoO4 and commonly used salts in SCs.
KI. Sathyamoorthi reported on a viologen-based redox active Kim et al. (2016) reported a high-performance flexible
electrolyte, in which the redox behavior of bromide and 1,1′ - microcapacitor, which employed a poly(methyl methacrylate)-
diethyl-4,4′ -bipyridinium ions boosted both anode and cathode propylene carbonate-lithium perchlorate (PMMA-PC-LiClO4 )
performance (Sathyamoorthi et al., 2016). Interestingly, the electrolyte with hydroquinone (HQ) redox additive. The
specific capacitance of the SCs increases continuously during the operating voltage of this system is up to 1.2 V, which is better
charge and discharge cycle, and a 30% increase is observed at than that of other flexible SCs under HQ-PVA-H2 SO4 and
the end of the 1,000 cycles. Hu et al. (2017) reported on redox PPD-PVA-KOH electrolytes (both below 1 V). The volumetric
additives 4-hydroxybenzoic acid (HBA), 3,4-dihydroxybenzoic capacitance increased 35-fold due to the reversible redox reaction
acid (DHBA), and 3,4,5-trihydroxybenzoic acid (THBA) in between hydroquinone (HQ) and benzoquinone (BQ). Also, a
H2 SO4 . SCs with HBA and DHBA exhibit higher capacitances flexible SC with an extended operating voltage of 1.5 V, a specific
because of their functional hydroxyl groups in the benzene ring. capacitance of up to 363 F g−1 , and an energy density of 27.4 Wh
For alkaline electrolytes, K3 Fe(CN)6 (Veerasubramani et al., kg−1 was obtained under an organic electrolyte with ferrocene
2016; Lamiel et al., 2017) and p-phenylenediamine (PPD) (Zhang and 4-oxo-2, 2, 6, 6-tetramethylpiperidinooxy additive, due to
et al., 2015) can improve the capacitance and stability of the the wide voltage of the organic electrolyte and the additional
SCs. Zhang et al. (2015) introduced PPD into KOH electrolytes faraday capacitance from the redox mediator (Zhang et al.,

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Zhang et al. Redox Electrolytes for Supercapacitors

2016). Dall’Agnese et al. (2016) studied the electrochemical energy density is as high as 13.2 Wh kg−1 , while the self-discharge
behavior of two-dimensional titanium carbide (MXene) at the positive electrode is fully suppressed due to the deposition
in acetonitrile solution with 1-ethyl-3-methylimidazolium of a film on the electrode. It can be seen that redox-mediated ionic
bis(trifluoromethylsulfonyl)imide (EMITFSI) additive. The liquid electrolytes are promising alternatives to conventional
capacitance of 85 F g−1 was obtained at 2 mV s−1 , while a high electrolytes. However, the problems of liquid electrolyte leakage
rate capability and good cyclability appeared. Through in-situ and corrosion in liquid electrolytes have severely limited its
X-ray diffraction studies, it was found that EMI+ cations are application (Ma et al., 2015).
embedded in MXene, which results in increased capacitance.

REDOX MEDIATED GEL ELECTROLYTES

REDOX MEDIATED IONIC LIQUID
ELECTROLYTES GEL is a special material between liquid and solid, which
exhibits the flexibility and stability of solid and the easy diffusion
Ionic liquids are generally composed of a bulky, asymmetric of liquid (Zhi-yu et al., 2019). It has a series of advantages
organic cation and a weakly coordinating inorganic/organic such as a higher ionic conductivity than solid electrolytes and
anion, which shows a wide electrochemical window (generally good mechanical and chemical stability, etc., which makes it a
above 3.5 V), high electrochemical stability, good oxidation promising electrolyte (Batisse and Raymundo-Piñero, 2017; Qin
resistance, and so on (Brandt et al., 2013). In recent years, it was and Panzer, 2017; Hui et al., 2019; Li et al., 2019). Recently, a
discovered that Quinones are excellent redox electrolyte additives novel redox-mediated strategy for SCs was reported, which can
in ionic liquid electrolytes. The introduction of hydroquinone efficiently increase the ionic conductivity and produce additional
(HQ) (Dubal et al., 2015; Sathyamoorthi et al., 2015; Xu et al., capacitance by the quick reversible redox reaction introduced by
2015) and benzoquinone (BQ) (Navalpotro et al., 2016) into the the redox mediator (Alipoori et al., 2020). The redox additives
electrolyte as organic redox shuttles leads to low charge transfer in gel polymer electrolytes usually include indigo carmine (IC)
resistance and contributes to the improvement of the specific (Ma et al., 2015), 2-mercaptopyridine (PySH) (Pan et al., 2015),
capacitance and specific energy of SCs. 1-butyl-3-methylimidazolium iodide (BMIMI) (Tu et al., 2018),
In addition, it is reported that the addition of tin sulfate alizarin red S (ARS) (Sun et al., 2016), FeBr3 (Wang et al., 2019),
(SnSO4 ) and vanadium sulfate (VOSO4 ) (Lee et al., 2016b) to 1,4 Naphthoquinone (Hashemi et al., 2018), 1-anthraquinone
the ionic liquid electrolyte can also significantly improve the sulfonic acid sodium (AQQS) (Feng et al., 2016) and 1-ethyl-3-
overall performance of the SCs. Xie H. J. et al. (2016) reported methylimidazolium tetrafluoroborate ([EMIM]BF4 ) (Seok Jang
two redox ionic liquids, [FcEIm][NTf2 ] and [EMIm][FcNTf], et al., 2016).
which were prepared by modifying either the [EMIm] cation or The redox-mediated gel polymer electrolyte (PVA-H2 SO4 -IC)
the [NTf2 ] anion with ferrocene. Based on [EMIm][FcNTf], the was prepared by adding indigo carmine (IC) to a mixture of

FIGURE 1 | (A) The fabrication model of the SCs with PVA-H2 SO4 -ARS electrolyte, (B) double-layer formation and redox reaction on the carbon surface, (C) CV
curves for the SCs at 10 mV s−1 , (D) Ragone plots of the SCs with PVA-H2 SO4 -ARS electrolyte, (E) cyclic performances of the SCs with PVA-H2 SO4 -ARS electrolyte
at 1 A g−1 . Reproduced by permission of The Royal Society of Chemistry from Sun et al. (2016).

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Zhang et al. Redox Electrolytes for Supercapacitors

polyvinyl alcohol (PVA) and sulfuric acid (H2 SO4 ). Its ionic Sun et al. (2015a) prepared a redox-mediated gel polymer-
conductivity is increased by 188%, reaching 20.27 mS cm−1 . Due polyvinyl alcohol-orthophosphate 2-mercaptopyridine (PVA-
to the reversible redox reaction of the IC, the specific capacitance H3 PO4 -PySH) by introducing PySH into PVA-H3 PO4 . The ionic
of the device was increased by 112.2% (382 F g−1 ), and the conductivity of the PVA-H3 PO4 -PySH system was increased
energy density also increased to 13.26 Wh kg−1 . It also shows by 92% to 22.57 mS cm−1 . As a result, a high specific
excellent cycling stability (80.3% capacitance retention after capacitance (1,128 F g−1 ) and energy density (39.17 Wh kg−1 )
3,000 cycles) (Ma et al., 2015). When alizarin red S (ARS) was were obtained. These improved properties are attributed to
added into polyvinyl alcohol-sulfuric acid (PVA-H2 SO4 ), a new the redox reaction between PySH and 2,2′ -bipyridine redox
type of electrolyte (PVA-H2 SO4 -ARS) was obtained (Figure 1). couple in PVA-H3 PO4 -PySH (Ye et al., 2018). These results
Its conductivity reached 33.3 mS cm−1 , due to ARS acting as undoubtedly indicate that redox-mediated gel polymers are
a redox shuttle in the electrolyte. Compared with ARS-free promising electrolyte candidates for advanced flexible SCs
SCs (160 F g−1 at 0.5 A g−1 ), the specific capacitance of SCs (Aljafari et al., 2019).
using a PVA-H2 SO4 -ARS gel polymer electrolyte is larger (441 F Although redox electrolytes have greatly contributed to the
g−1 at 0.5 A g−1 ). At the same time, its energy density is as improvement of the performance of SCs, it’s worth noting
high as 39.4 Wh kg−1 and it has a good cycling stability. that self-discharge (SD) is a fatal weakness for most redox
Therefore, the redox-mediated electrolyte has a good application electrolytes. So, many pieces of research have focused on
prospect in improving the electrochemical performance of SCs this problem recently. Fan et al. (2020) lowered self-discharge
(Sun et al., 2016). and improved energy density and cycling stability (capacitance

TABLE 1 | Redox electrolyte-based SCs and their performance (Mai et al., 2013; Park et al., 2014; Yu et al., 2014; Díaz et al., 2015; Sathyamoorthi et al., 2015; Zhang
et al., 2015; Kim et al., 2016; Navalpotro et al., 2016; Seok Jang et al., 2016; Singh and Chandra, 2016; Xie H. J. et al., 2016; Mousavi et al., 2017; Ren et al., 2017; Gao
et al., 2018; Tu et al., 2018; Wang et al., 2019).

Redox additives Supporting Capacitance Energy density Cycling stability

electrolyte (Wh kg−1 )

Redox mediated aqueous KI H2 SO4 203–616 F g−1 at 1 A g−1 — 77.3% capacitance

electrolytes retention after 5,000 cycles
Ce2 (SO4 )3 H2 SO4 408 F g−1 at 17.7 mA 1.24–13.84 94% capacitance retention
cm−2 after 3,000 cycles
0.8 M Fe3+ /Fe2+ H2 SO4 1,062 F g−1 at 2 A g−1 8.3–22.1 93% capacitance retention
(almost tripled) after 10,000 cycles
Catechol H2 SO4 429–1,967 F g−1 at 1 A 81.8 80% capacitance retention
g−1 after 5,000 cycles
CuCl2 HNO3 440–4,700 F g−1 at 5 163 99.4% capacitance
mVs−1 retention after 5,000 cycles
PPD KOH 119.2–501.4 F g−1 at 3 A — 85.2% capacitance
g−1 retention after 5,000 cycles
KI Li2 SO4 96–198 F g−1 at 1 A g−1 65 85.3% capacitance
retention after 3,000 cycles
Redox mediated organic HQ PMMA 0.2–7.1 mF cm−2 at — 97% capacitance retention
electrolytes 0.1 mA cm−2 after 10,000 cycles
PPD LiClO4 +AC 25–69 F g−1 at 0.5 A g−1 18–54 93% capacitance retention
after 5,000 cycles
DmFc TBAP+THF 8.3–61.3 F g−1 at 10 A 36.8 88.4% capacitance
g−1 retention after 10,000 cycles
Redox mediated ionic HQ TEATFSI 72 F g−1 at 0.57 mA cm−2 18.4–31.22 84.1% capacitance
electrolytes retention after 1,000 cycles
p-BQ PYR14 TFSI 20–70 F g−1 at 5 mA cm−2 3.5–10.3 50% capacitance retention
after 1,000 cycles
Ferrocene [EMIM] [NTf2 ] — 7.2–13.2 —
Redox mediated gel FeBr3 H2 SO4 +PVA 204–885 F g−1 33.9 100% capacitance retention
electrolytes after 10,000 cycles
BMIMI Li2 SO4 +PVA 139.1–384 F g−1 at 0.25 A 10.4–29.3 80.9% capacitance
g−1 retention after 10,000 cycles
[EMIM]BF4 H3 PO4 + PVA 103–271 F g−1 at 0.5 A 20.7–54.3 70% capacitance retention
g−1 after 3,000 cycles

EVD, ethyl viologen dibromide; AQDS, anthraquinone-2,7-disulphonate; PMMA, poly (methyl methacrylate); DmFc, decamethylferrocene; TBAP, tetrabutylammonium perchlorate;
THF, tetrahydrofuran; TEATFSI, triethylammonium bis(trifluoromethane)sulfonamide; p-BQ, para-benzoquinone; PYR14 TFSI, N-butyl-N-methyl pyrro lidinium bis(trifluoromethanesulfonyl)
imide; [EMIM][NTf2 ], 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide.

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Zhang et al. Redox Electrolytes for Supercapacitors

retention 87.9% after 10,000 cycles) by the addition of Li2 SO4 - the overall performance of SCs, we can start from the following
BMIMBr-carbon nanotubes in the PVA solution, in which the aspects: (1) The introduction of redox active materials that
3D carbon nanotubes networks provide fast ion transmission can produce reversible redox reactions in the electrolyte is
channels. Chen et al. (2014) blocked the migration of the an effective way to increase the capacity and energy density
active electrolyte between two electrodes and suppressed the of SCs; (2) Investigating the interaction mechanism between
self-discharge though inhibiting BQ shuttle with Nafion R
177 the electrode material and the electrolyte, and optimizing the
membrane or suppressing shuffle effect with a CuSO4 active matching relationship between them. Taken together, these redox
electrolyte. It is believed that these results will guide the further electrolytes pave the way for high-performance SCs applications.
design of SCs with both a high energy density and good
energy retention. AUTHOR CONTRIBUTIONS
In the end, a table (Table 1) was given, in which several typical
redox electrolyte-based SCs are summarized and compared All authors listed have made a substantial, direct and intellectual
for clarity. contribution to the work, and approved it for publication.

CONCLUSIONS AND PERSPECTIVES FUNDING

Each redox electrolyte has its own advantages and disadvantages. This work was supported by National Natural Science
The two most important criteria for selecting an electrolyte are Foundation (51702123, 51872161), Shandong Province Higher
the operating voltage and the ionic conductivity. The higher Educational Youths Innovation Science and Technology
the operating voltage and the ionic conductivity is, the greater Program (2019KJA018), and the Educational Commission of
the energy density and power density of the SCs. In order to Anhui Province of China (KJ2019A0868). SY thanks University
further develop high-performance SCs electrolytes and improve of Jinan Start-up Research Funding.

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performance carbon nanotube based fiber-shaped supercapacitors using redox Conflict of Interest: The authors declare that the research was conducted in the
additives of polypyrrole and hydroquinone. J. Mater. Chem. A 3, 22353–22360. absence of any commercial or financial relationships that could be construed as a
doi: 10.1039/C5TA06165B potential conflict of interest.
Yang, W., Yang, W., Song, A., Gao, L., Su, L., and Shao, G. (2017).
Supercapacitance of nitrogen-sulfur-oxygen co-doped 3D hierarchical porous Copyright © 2020 Zhang, Yang, Chang, Zhao, Wang, Yang and Cao. This is an
carbon in aqueous and organic electrolyte. J. Power Sources 359, 556–567. open-access article distributed under the terms of the Creative Commons Attribution
doi: 10.1016/j.jpowsour.2017.05.108 License (CC BY). The use, distribution or reproduction in other forums is permitted,
Ye, T., Li, D., Liu, H., She, X., Xia, Y., Zhang, S., et al. (2018). provided the original author(s) and the copyright owner(s) are credited and that the
Seaweed biomass-derived flame-retardant gel electrolyte membrane original publication in this journal is cited, in accordance with accepted academic
for safe solid-state supercapacitors. Macromolecules 51, 9360–9367. practice. No use, distribution or reproduction is permitted which does not comply
doi: 10.1021/acs.macromol.8b01955 with these terms.

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