Electrolyte Engineering in Redox-Enhanced Electrochemical Capacitors with Zn Anodes: The Role of Colorimetric Indicators
Corresponding Author: Kaiyuan Shi
Nano-Micro Letters,
Vol. 18 (2026), Article Number: 267
Abstract
The increasing demand for high-performance energy devices has prompted the exploration of advanced electrolytic solutions for aqueous energy storage. Redox-enhanced Zn-ion capacitors (RZICs) overcome the limitations of conventional electrochemical capacitors by integrating redox-active molecules into the electrolyte, which enables higher energy density and expanded voltage windows. In this study, we developed organic dye-based colorimetric indicators for the fabrication of functional electrolytes in RZICs. The structural responsiveness of these dyes, driven by proton–electron transfer through electrochromic dynamics, allows real-time monitoring and optimization of the RZICs. The acid–base equilibrium of colorimetric indicators supports pH buffering, resulting in an extended lifespan of Zn||Zn cells up to 4,000 h. The conjugated aromatic structure of the indicators enhances their adsorption onto activated carbon, thereby minimizing the self-discharge in RZICs. Additionally, the phenol–quinone transformation increases the capacity of RZICs to 152.4 mAh g−1 within an optimized voltage window of 0.2–1.6 V, while promoting electrochemical kinetics and suppressing anode degradation. The results advance the design and customization of redox electrolytes with colorimetric properties for supercapacitive energy storage.
Highlights:
1 Triphenylmethane dyes as colorimetric indicators were developed for fabricating functional electrolytes in redox-enhanced zinc-ion hybrid capacitors (RZICs), integrating pH buffering, electrochromic response, and redox activity.
2 The colorimetric indicators exhibit proton-electron transfer behavior, where proton transfer enables health state diagnostics and electron transfer facilitates reversible redox reactions.
3 The dye-containing electrolytes provide a wider voltage window, high capacity, and long cycling stability for high-performance RZIC devices.
4 Incorporating colorimetric indicators extends the cycling lifespan of Zn||Zn cells to 4,000 h, allowing RZICs to deliver a capacity of 152.4 mAh g−1 within a 0.2-1.6 V voltage window, with 87.7% capacity retention after 20,000 cycles.
Keywords
Download Citation
Endnote/Zotero/Mendeley (RIS)BibTeX
- Y.S. Meng, V. Srinivasan, K. Xu, Designing better electrolytes. Science 378(6624), eabq3750 (2022). https://doi.org/10.1126/science.abq3750
- Y.-H. Zhu, Y.-F. Cui, Z.-L. Xie, Z.-B. Zhuang, G. Huang et al., Decoupled aqueous batteries using pH-decoupling electrolytes. Nat. Rev. Chem. 6(7), 505–517 (2022). https://doi.org/10.1038/s41570-022-00397-3
- N. Govindarajan, A. Xu, K. Chan, How pH affects electrochemical processes. Science 375(6579), 379–380 (2022). https://doi.org/10.1126/science.abj2421
- M. Shi, P. Das, Z.-S. Wu, T.-G. Liu, X. Zhang, Aqueous organic batteries using the proton as a charge carrier. Adv. Mater. 35(42), 2302199 (2023). https://doi.org/10.1002/adma.202302199
- Y. Liu, P. Zhang, Z. Wu, J. Wei, G. Ding et al., Screening ultra-stable (phenazine)dioxyalkanocic acids with varied water-solubilizing chain lengths for high-capacity aqueous redox flow batteries. J. Am. Chem. Soc. 146(5), 3293–3302 (2024). https://doi.org/10.1021/jacs.3c11887
- M. Luo, X. Gan, C. Zhang, Y. Yang, W. Yue et al., Overcoming obstacles in Zn-ion batteries development: application of conductive redox-active polypyrrole/Tiron anolyte interphase. Adv. Funct. Mater. 33(47), 2305041 (2023). https://doi.org/10.1002/adfm.202305041
- M. Chen, L. Gong, I. Zhitomirsky, K. Shi, Unraveling the dynamic transformation of azobenzene-driven redox electrolytes for Zn-ion hybrid capacitors. Energy Environ. Sci. 18(9), 4460–4469 (2025). https://doi.org/10.1039/d4ee05696e
- M. Chen, R. Chen, I. Zhitomirsky, G. He, K. Shi, Redox-active molecules for aqueous electrolytes of energy storage devices: a review on fundamental aspects, current progress, and prospects. Mater. Sci. Eng. R. Rep. 161, 100865 (2024). https://doi.org/10.1016/j.mser.2024.100865
- K. Yang, T. Zhang, Q. Li, Z. Peng, J. Ning et al., Assembling-induced redox property adjustment of Fe(III)/Fe(IV) electroredox couple-based commercial dye catholyte via bio-inspired multicoordination sphere construction strategy for stable aqueous redox flow batteries. Energy Storage Mater. 71, 103648 (2024). https://doi.org/10.1016/j.ensm.2024.103648
- Z. Zhao, X. Liu, M. Zhang, L. Zhang, C. Zhang et al., Development of flow battery technologies using the principles of sustainable chemistry. Chem. Soc. Rev. 52(17), 6031–6074 (2023). https://doi.org/10.1039/D2CS00765G
- Q. Wang, T. O’Carroll, F. Shi, Y. Huang, G. Chen et al., Designing organic material electrodes for lithium-ion batteries: progress, challenges, and perspectives. Electrochem. Energy Rev. 7(1), 15 (2024). https://doi.org/10.1007/s41918-024-00218-9
- D.F. Duxbury, The photochemistry and photophysics of triphenylmethane dyes in solid and liquid media. Chem. Rev. 93(1), 381–433 (1993). https://doi.org/10.1021/cr00017a018
- D.-S. Liu, Z. Zhang, Y. Zhang, M. Ye, S. Huang et al., Manipulating OH--mediated anode-cathode cross-communication toward long-life aqueous zinc-vanadium batteries. Angew. Chem. Int. Ed. 62(5), e202215385 (2023). https://doi.org/10.1002/anie.202215385
- A.G. Tamirat, X. Guan, J. Liu, J. Luo, Y. Xia, Redox mediators as charge agents for changing electrochemical reactions. Chem. Soc. Rev. 49(20), 7454–7478 (2020). https://doi.org/10.1039/d0cs00489h
- C.F. Bischoff, O.S. Fitz, J. Burns, M. Bauer, H. Gentischer et al., Revealing the local pH value changes of acidic aqueous zinc ion batteries with a manganese dioxide electrode during cycling. J. Electrochem. Soc. 167(2), 020545 (2020). https://doi.org/10.1149/1945-7111/ab6c57
- D. Perez-Antolin, I. Sáez-Bernal, A. Colina, E. Ventosa, Float-charging protocol in rechargeable Zn–MnO2 batteries: unraveling the key role of Mn2+ additives in preventing spontaneous pH changes. Electrochem. Commun. 138, 107271 (2022). https://doi.org/10.1016/j.elecom.2022.107271
- M. Pei, X. Jin, R. Mao, D. Liu, C. Su et al., Decoupling self-matching effect between cathode and anode in hybrid electrochemical capacitors. Adv. Mater. 37(32), e2507061 (2025). https://doi.org/10.1002/adma.202507061
- Y. Zhu, S. Deebansok, J. Deng, X. Wang, T. Brousse et al., Electron delocalization and electrochemical potential distribution phenomena in faradaic electrode materials for understanding electrochemical behavior. Adv. Energy Mater. 14(22), 2304317 (2024). https://doi.org/10.1002/aenm.202304317
- X. Gan, J. Tang, X. Wang, L. Gong, I. Zhitomirsky et al., Aromatic additives with designed functions ameliorating chemo-mechanical reliability for zinc-ion batteries. Energy Storage Mater. 59, 102769 (2023). https://doi.org/10.1016/j.ensm.2023.102769
- S. Chen, K. Ouyang, Y. Liu, H. Qin, M. Cui et al., Strong metal-support interaction to invert hydrogen evolution overpotential of Cu coating for high-coulombic-efficiency stable Zn anode in aqueous Zn-ion batteries. Adv. Mater. 37(15), 2417775 (2025). https://doi.org/10.1002/adma.202417775
- Y. Chen, Z. Deng, Y. Sun, Y. Li, H. Zhang et al., Ultrathin zincophilic interphase regulated electric double layer enabling highly stable aqueous zinc-ion batteries. Nano-Micro Lett. 16(1), 96 (2024). https://doi.org/10.1007/s40820-023-01312-1
- B. Evanko, S.W. Boettcher, S.J. Yoo, G.D. Stucky, Redox-enhanced electrochemical capacitors: status, opportunity, and best practices for performance evaluation. ACS Energy Lett. 2(11), 2581–2590 (2017). https://doi.org/10.1021/acsenergylett.7b00828
- J. Byeon, J. Ko, S. Lee, D.H. Kim, S.W. Kim et al., Solubility-enhancing hydrotrope electrolyte with tailor-made organic redox-active species for redox-enhanced electrochemical capacitors. ACS Energy Lett. 8(5), 2345–2355 (2023). https://doi.org/10.1021/acsenergylett.3c00254
- J. Wang, J. Polleux, J. Lim, B. Dunn, Pseudocapacitive contributions to electrochemical energy storage in TiO2 (anatase) nanops. J. Phys. Chem. C 111(40), 14925–14931 (2007). https://doi.org/10.1021/jp074464w
- Y. Chen, Z. Song, Y. Lv, L. Gan, M. Liu, NH4+-modulated cathodic interfacial spatial charge redistribution for high-performance dual-ion capacitors. Nano-Micro Lett. 17(1), 117 (2025). https://doi.org/10.1007/s40820-025-01660-0
- Y. Li, X. Li, X. Peng, X. Yang, F. Kang et al., Electrolyte additive-assembled interconnecting molecules-zinc anode interface for zinc-ion hybrid supercapacitors. Nano-Micro Lett. 17(1), 268 (2025). https://doi.org/10.1007/s40820-025-01794-1
- L. Wei, Y. Chen, Z. Huang, S. Zheng, X. Guo, Redox-enhanced zinc-ion hybrid capacitors with high energy density enabled by high-voltage active aqueous electrolytes based on low salt concentration. Energy Storage Mater. 58, 30–39 (2023). https://doi.org/10.1016/j.ensm.2023.03.015
- X. Gan, C. Zhang, X. Ye, L. Qie, K. Shi, Unveiling the potential of redox electrolyte additives in enhancing interfacial stability for Zn-ion hybrid capacitors. Energy Storage Mater. 65, 103175 (2024). https://doi.org/10.1016/j.ensm.2024.103175
- L. Zhang, C. Zhang, E.J. Berg, Mastering proton activities in aqueous batteries. Adv. Mater. 37(23), 2407852 (2025). https://doi.org/10.1002/adma.202407852
- S. Sariyer, S. Yeşilot, N. Kılıç, A. Ghosh, O. Sel et al., Polyphosphazene based inorganic-organic hybrid cathode containing pyrene tetraone sides for aqueous zinc-ion batteries. Batter. Supercaps 6(4), e202200529 (2023). https://doi.org/10.1002/batt.202200529
- Q. Wang, Y.F. Nie, X.Y. Chen, Z.H. Xiao, Z.J. Zhang, Use of pyrocatechol violet as an effective redox additive for highly promoting the supercapacitor performances. J. Power. Sources 323, 8–16 (2016). https://doi.org/10.1016/j.jpowsour.2016.05.010
- M. Luo, X. Gan, X. Zhao, L. Huang, H. Zhu et al., A dendrite suppression coating formulated via electrophoretic deposition using bi-functional surfactants for Zn-ion batteries. J. Alloys Compd. 918, 165790 (2022). https://doi.org/10.1016/j.jallcom.2022.165790
- J. Wang, M. Chen, D. Shao, I. Zhitomirsky, K. Shi, Zn-ion hybrid capacitors utilizing redox electrolytes derived from naphthoquinone molecules. Mater. Today Energy 51, 101893 (2025). https://doi.org/10.1016/j.mtener.2025.101893
- C. Xiao, Q. Luo, I. Zhitomirsky, G. He, K. Shi, Organic dyes and dye derivatives for advanced electrochemical energy storage: a review of sustainable and emerging materials. Coord. Chem. Rev. 555, 217659 (2026). https://doi.org/10.1016/j.ccr.2026.217659
- R. Sun, D. Han, C. Cui, Z. Han, X. Guo et al., A self-deoxidizing electrolyte additive enables highly stable aqueous zinc batteries. Angew. Chem. Int. Ed. 62(28), e202303557 (2023). https://doi.org/10.1002/anie.202303557
- M.T.M. Koper, Theory of the transition from sequential to concerted electrochemical proton–electron transfer. Phys. Chem. Chem. Phys. 15(5), 1399–1407 (2013). https://doi.org/10.1039/C2CP42369C
- N.B. Lewis, R.P. Bisbey, K.S. Westendorff, A.V. Soudackov, Y. Surendranath, A molecular-level mechanistic framework for interfacial proton-coupled electron transfer kinetics. Nat. Chem. 16(3), 343–352 (2024). https://doi.org/10.1038/s41557-023-01400-0
- D. Lei, W. Shang, L. Cheng, Poonam, W. Kaiser et al., Ion-transport kinetics and interface stability augmentation of zinc anodes based on fluorinated covalent organic framework thin films. Adv. Energy Mater. 14(46), 2403030 (2024). https://doi.org/10.1002/aenm.202403030
- B. Wang, C. Guan, Q. Zhou, Y. Wang, Y. Zhu et al., Screening anionic groups within zwitterionic additives for eliminating hydrogen evolution and dendrites in aqueous zinc ion batteries. Nano-Micro Lett. 17(1), 314 (2025). https://doi.org/10.1007/s40820-025-01826-w
- L. Jiang, Y. Ding, L. Li, Y. Tang, P. Zhou et al., Cationic adsorption-induced microlevelling effect: a pathway to dendrite-free zinc anodes. Nano-Micro Lett. 17(1), 202 (2025). https://doi.org/10.1007/s40820-025-01709-0
- Y. Dai, H. He, M. Ouyang, J. Chen, J. Lin et al., In-operando X-ray imaging for sobering examination of aqueous zinc metal batteries. Nano-Micro Letters 18(1), 85 (2025). https://doi.org/10.1007/s40820-025-01911-0
- M. Kim, J. Lee, Y. Kim, Y. Park, H. Kim et al., Surface overpotential as a key metric for the discharge–charge reversibility of aqueous zinc-ion batteries. J. Am. Chem. Soc. 145(29), 15776–15787 (2023). https://doi.org/10.1021/jacs.3c01614
- S.S. Hemdan, A.M.A.L. Gebali, F.K. Ali, The electrostatic and non-electrostatic interaction affect on acidity constants of bromocresol purple in aqueous ethanolic media. J. Solution Chem. 53(6), 761–772 (2024). https://doi.org/10.1007/s10953-023-01270-7
- N. Kari, S. Koxmak, K. Wumaier, P. Nizamidin, S. Abliz et al., Application of bromocresol purple nanofilm and laser light to detect mutton freshness. Spectrochim. Acta A Mol. Biomol. Spectrosc. 244, 118863 (2021). https://doi.org/10.1016/j.saa.2020.118863
- I.M. Steinberg, A. Lobnik, O.S. Wolfbeis, Characterisation of an optical sensor membrane based on the metal ion indicator Pyrocatechol Violet. Sens. Actuators B Chem. 90(1–3), 230–235 (2003). https://doi.org/10.1016/S0925-4005(03)00033-9
- H. Gan, H. Li, M. Xu, C. Han, H.-M. Cheng, Failure mechanisms and remedy of an ultrathin Zn metal anode in pouch cells. Joule 8(11), 3054–3071 (2024). https://doi.org/10.1016/j.joule.2024.07.013
- T. Yan, B. Wu, S. Liu, M. Tao, J. Liang et al., Sieving-type electric double layer with hydrogen bond interlocking to stable zinc metal anode. Angew. Chem. Int. Ed. 63(47), e202411470 (2024). https://doi.org/10.1002/anie.202411470
- J. Zhou, F. Wu, Y. Mei, Y. Hao, L. Li et al., Establishing thermal infusion method for stable zinc metal anodes in aqueous zinc-ion batteries. Adv. Mater. 34(21), 2200782 (2022). https://doi.org/10.1002/adma.202200782
- H.P. de Oliveira, Determination of pKa of dyes by electrical impedance spectroscopy. Microchem. J. 88(1), 32–37 (2008). https://doi.org/10.1016/j.microc.2007.09.002
- E. Hudson-Heck, X. Liu, R.H. Byrne, Purification and physical-chemical characterization of bromocresol purple for carbon system measurements in freshwaters, estuaries, and oceans. ACS Omega 6(28), 17941–17951 (2021). https://doi.org/10.1021/acsomega.1c01579
- X. Sun, X. Zhang, K. Wang, Y. An, X. Zhang et al., Determination strategy of stable electrochemical operating voltage window for practical lithium-ion capacitors. Electrochim. Acta 428, 140972 (2022). https://doi.org/10.1016/j.electacta.2022.140972
- K. Xu, S.P. Ding, T.R. Jow, Toward reliable values of electrochemical stability limits for electrolytes. J. Electrochem. Soc. 146(11), 4172–4178 (1999). https://doi.org/10.1149/1.1392609
- D. Weingarth, H. Noh, A. Foelske-Schmitz, A. Wokaun, R. Kötz, A reliable determination method of stability limits for electrochemical double layer capacitors. Electrochim. Acta 103, 119–124 (2013). https://doi.org/10.1016/j.electacta.2013.04.057
- C. Ding, T. Huang, Y. Tao, D. Tan, Y. Zhang et al., Identifying the origin and contribution of pseudocapacitive sodium ion storage in tungsten disulphide nanosheets for application in sodium-ion capacitors. J. Mater. Chem. A 6(42), 21010–21017 (2018). https://doi.org/10.1039/C8TA07677D
- W. Fan, L. Qin, S. Alshammari, M.H. Helal, Z.M. El-Bahy et al., Opportunities for aqueous electrolytic zinc–manganese batteries. ACS Energy Lett. 10(8), 3914–3921 (2025). https://doi.org/10.1021/acsenergylett.5c01631
- W. Fan, L. Qin, T.F. Altamimi, Z.M. El-Bahy, B. Lu et al., Redox mediators for aqueous electrolytic zinc-manganese batteries: fundamentals and design criteria. Adv. Energy Mater. 16(2), e04251 (2026). https://doi.org/10.1002/aenm.202504251
- S.-E. Chun, B. Evanko, X. Wang, D. Vonlanthen, X. Ji et al., Design of aqueous redox-enhanced electrochemical capacitors with high specific energies and slow self-discharge. Nat. Commun. 6, 7818 (2015). https://doi.org/10.1038/ncomms8818
- G. Shul, D. Bélanger, Self-discharge of electrochemical capacitors based on soluble or grafted quinone. Phys. Chem. Chem. Phys. 18(28), 19137–19145 (2016). https://doi.org/10.1039/c6cp02356h
- C. Cougnon, Exploring the interdependence between the coulombic, voltage and energy efficiencies. Electrochem. Commun. 120, 106832 (2020). https://doi.org/10.1016/j.elecom.2020.106832
- M.C.G. Santos, G.G. Silva, R. Santamaría, P.F.R. Ortega, R.L. Lavall, Discussion on operational voltage and efficiencies of ionic-liquid-based electrochemical capacitors. J. Phys. Chem. C 123(14), 8541–8549 (2019). https://doi.org/10.1021/acs.jpcc.8b11607
References
Y.S. Meng, V. Srinivasan, K. Xu, Designing better electrolytes. Science 378(6624), eabq3750 (2022). https://doi.org/10.1126/science.abq3750
Y.-H. Zhu, Y.-F. Cui, Z.-L. Xie, Z.-B. Zhuang, G. Huang et al., Decoupled aqueous batteries using pH-decoupling electrolytes. Nat. Rev. Chem. 6(7), 505–517 (2022). https://doi.org/10.1038/s41570-022-00397-3
N. Govindarajan, A. Xu, K. Chan, How pH affects electrochemical processes. Science 375(6579), 379–380 (2022). https://doi.org/10.1126/science.abj2421
M. Shi, P. Das, Z.-S. Wu, T.-G. Liu, X. Zhang, Aqueous organic batteries using the proton as a charge carrier. Adv. Mater. 35(42), 2302199 (2023). https://doi.org/10.1002/adma.202302199
Y. Liu, P. Zhang, Z. Wu, J. Wei, G. Ding et al., Screening ultra-stable (phenazine)dioxyalkanocic acids with varied water-solubilizing chain lengths for high-capacity aqueous redox flow batteries. J. Am. Chem. Soc. 146(5), 3293–3302 (2024). https://doi.org/10.1021/jacs.3c11887
M. Luo, X. Gan, C. Zhang, Y. Yang, W. Yue et al., Overcoming obstacles in Zn-ion batteries development: application of conductive redox-active polypyrrole/Tiron anolyte interphase. Adv. Funct. Mater. 33(47), 2305041 (2023). https://doi.org/10.1002/adfm.202305041
M. Chen, L. Gong, I. Zhitomirsky, K. Shi, Unraveling the dynamic transformation of azobenzene-driven redox electrolytes for Zn-ion hybrid capacitors. Energy Environ. Sci. 18(9), 4460–4469 (2025). https://doi.org/10.1039/d4ee05696e
M. Chen, R. Chen, I. Zhitomirsky, G. He, K. Shi, Redox-active molecules for aqueous electrolytes of energy storage devices: a review on fundamental aspects, current progress, and prospects. Mater. Sci. Eng. R. Rep. 161, 100865 (2024). https://doi.org/10.1016/j.mser.2024.100865
K. Yang, T. Zhang, Q. Li, Z. Peng, J. Ning et al., Assembling-induced redox property adjustment of Fe(III)/Fe(IV) electroredox couple-based commercial dye catholyte via bio-inspired multicoordination sphere construction strategy for stable aqueous redox flow batteries. Energy Storage Mater. 71, 103648 (2024). https://doi.org/10.1016/j.ensm.2024.103648
Z. Zhao, X. Liu, M. Zhang, L. Zhang, C. Zhang et al., Development of flow battery technologies using the principles of sustainable chemistry. Chem. Soc. Rev. 52(17), 6031–6074 (2023). https://doi.org/10.1039/D2CS00765G
Q. Wang, T. O’Carroll, F. Shi, Y. Huang, G. Chen et al., Designing organic material electrodes for lithium-ion batteries: progress, challenges, and perspectives. Electrochem. Energy Rev. 7(1), 15 (2024). https://doi.org/10.1007/s41918-024-00218-9
D.F. Duxbury, The photochemistry and photophysics of triphenylmethane dyes in solid and liquid media. Chem. Rev. 93(1), 381–433 (1993). https://doi.org/10.1021/cr00017a018
D.-S. Liu, Z. Zhang, Y. Zhang, M. Ye, S. Huang et al., Manipulating OH--mediated anode-cathode cross-communication toward long-life aqueous zinc-vanadium batteries. Angew. Chem. Int. Ed. 62(5), e202215385 (2023). https://doi.org/10.1002/anie.202215385
A.G. Tamirat, X. Guan, J. Liu, J. Luo, Y. Xia, Redox mediators as charge agents for changing electrochemical reactions. Chem. Soc. Rev. 49(20), 7454–7478 (2020). https://doi.org/10.1039/d0cs00489h
C.F. Bischoff, O.S. Fitz, J. Burns, M. Bauer, H. Gentischer et al., Revealing the local pH value changes of acidic aqueous zinc ion batteries with a manganese dioxide electrode during cycling. J. Electrochem. Soc. 167(2), 020545 (2020). https://doi.org/10.1149/1945-7111/ab6c57
D. Perez-Antolin, I. Sáez-Bernal, A. Colina, E. Ventosa, Float-charging protocol in rechargeable Zn–MnO2 batteries: unraveling the key role of Mn2+ additives in preventing spontaneous pH changes. Electrochem. Commun. 138, 107271 (2022). https://doi.org/10.1016/j.elecom.2022.107271
M. Pei, X. Jin, R. Mao, D. Liu, C. Su et al., Decoupling self-matching effect between cathode and anode in hybrid electrochemical capacitors. Adv. Mater. 37(32), e2507061 (2025). https://doi.org/10.1002/adma.202507061
Y. Zhu, S. Deebansok, J. Deng, X. Wang, T. Brousse et al., Electron delocalization and electrochemical potential distribution phenomena in faradaic electrode materials for understanding electrochemical behavior. Adv. Energy Mater. 14(22), 2304317 (2024). https://doi.org/10.1002/aenm.202304317
X. Gan, J. Tang, X. Wang, L. Gong, I. Zhitomirsky et al., Aromatic additives with designed functions ameliorating chemo-mechanical reliability for zinc-ion batteries. Energy Storage Mater. 59, 102769 (2023). https://doi.org/10.1016/j.ensm.2023.102769
S. Chen, K. Ouyang, Y. Liu, H. Qin, M. Cui et al., Strong metal-support interaction to invert hydrogen evolution overpotential of Cu coating for high-coulombic-efficiency stable Zn anode in aqueous Zn-ion batteries. Adv. Mater. 37(15), 2417775 (2025). https://doi.org/10.1002/adma.202417775
Y. Chen, Z. Deng, Y. Sun, Y. Li, H. Zhang et al., Ultrathin zincophilic interphase regulated electric double layer enabling highly stable aqueous zinc-ion batteries. Nano-Micro Lett. 16(1), 96 (2024). https://doi.org/10.1007/s40820-023-01312-1
B. Evanko, S.W. Boettcher, S.J. Yoo, G.D. Stucky, Redox-enhanced electrochemical capacitors: status, opportunity, and best practices for performance evaluation. ACS Energy Lett. 2(11), 2581–2590 (2017). https://doi.org/10.1021/acsenergylett.7b00828
J. Byeon, J. Ko, S. Lee, D.H. Kim, S.W. Kim et al., Solubility-enhancing hydrotrope electrolyte with tailor-made organic redox-active species for redox-enhanced electrochemical capacitors. ACS Energy Lett. 8(5), 2345–2355 (2023). https://doi.org/10.1021/acsenergylett.3c00254
J. Wang, J. Polleux, J. Lim, B. Dunn, Pseudocapacitive contributions to electrochemical energy storage in TiO2 (anatase) nanops. J. Phys. Chem. C 111(40), 14925–14931 (2007). https://doi.org/10.1021/jp074464w
Y. Chen, Z. Song, Y. Lv, L. Gan, M. Liu, NH4+-modulated cathodic interfacial spatial charge redistribution for high-performance dual-ion capacitors. Nano-Micro Lett. 17(1), 117 (2025). https://doi.org/10.1007/s40820-025-01660-0
Y. Li, X. Li, X. Peng, X. Yang, F. Kang et al., Electrolyte additive-assembled interconnecting molecules-zinc anode interface for zinc-ion hybrid supercapacitors. Nano-Micro Lett. 17(1), 268 (2025). https://doi.org/10.1007/s40820-025-01794-1
L. Wei, Y. Chen, Z. Huang, S. Zheng, X. Guo, Redox-enhanced zinc-ion hybrid capacitors with high energy density enabled by high-voltage active aqueous electrolytes based on low salt concentration. Energy Storage Mater. 58, 30–39 (2023). https://doi.org/10.1016/j.ensm.2023.03.015
X. Gan, C. Zhang, X. Ye, L. Qie, K. Shi, Unveiling the potential of redox electrolyte additives in enhancing interfacial stability for Zn-ion hybrid capacitors. Energy Storage Mater. 65, 103175 (2024). https://doi.org/10.1016/j.ensm.2024.103175
L. Zhang, C. Zhang, E.J. Berg, Mastering proton activities in aqueous batteries. Adv. Mater. 37(23), 2407852 (2025). https://doi.org/10.1002/adma.202407852
S. Sariyer, S. Yeşilot, N. Kılıç, A. Ghosh, O. Sel et al., Polyphosphazene based inorganic-organic hybrid cathode containing pyrene tetraone sides for aqueous zinc-ion batteries. Batter. Supercaps 6(4), e202200529 (2023). https://doi.org/10.1002/batt.202200529
Q. Wang, Y.F. Nie, X.Y. Chen, Z.H. Xiao, Z.J. Zhang, Use of pyrocatechol violet as an effective redox additive for highly promoting the supercapacitor performances. J. Power. Sources 323, 8–16 (2016). https://doi.org/10.1016/j.jpowsour.2016.05.010
M. Luo, X. Gan, X. Zhao, L. Huang, H. Zhu et al., A dendrite suppression coating formulated via electrophoretic deposition using bi-functional surfactants for Zn-ion batteries. J. Alloys Compd. 918, 165790 (2022). https://doi.org/10.1016/j.jallcom.2022.165790
J. Wang, M. Chen, D. Shao, I. Zhitomirsky, K. Shi, Zn-ion hybrid capacitors utilizing redox electrolytes derived from naphthoquinone molecules. Mater. Today Energy 51, 101893 (2025). https://doi.org/10.1016/j.mtener.2025.101893
C. Xiao, Q. Luo, I. Zhitomirsky, G. He, K. Shi, Organic dyes and dye derivatives for advanced electrochemical energy storage: a review of sustainable and emerging materials. Coord. Chem. Rev. 555, 217659 (2026). https://doi.org/10.1016/j.ccr.2026.217659
R. Sun, D. Han, C. Cui, Z. Han, X. Guo et al., A self-deoxidizing electrolyte additive enables highly stable aqueous zinc batteries. Angew. Chem. Int. Ed. 62(28), e202303557 (2023). https://doi.org/10.1002/anie.202303557
M.T.M. Koper, Theory of the transition from sequential to concerted electrochemical proton–electron transfer. Phys. Chem. Chem. Phys. 15(5), 1399–1407 (2013). https://doi.org/10.1039/C2CP42369C
N.B. Lewis, R.P. Bisbey, K.S. Westendorff, A.V. Soudackov, Y. Surendranath, A molecular-level mechanistic framework for interfacial proton-coupled electron transfer kinetics. Nat. Chem. 16(3), 343–352 (2024). https://doi.org/10.1038/s41557-023-01400-0
D. Lei, W. Shang, L. Cheng, Poonam, W. Kaiser et al., Ion-transport kinetics and interface stability augmentation of zinc anodes based on fluorinated covalent organic framework thin films. Adv. Energy Mater. 14(46), 2403030 (2024). https://doi.org/10.1002/aenm.202403030
B. Wang, C. Guan, Q. Zhou, Y. Wang, Y. Zhu et al., Screening anionic groups within zwitterionic additives for eliminating hydrogen evolution and dendrites in aqueous zinc ion batteries. Nano-Micro Lett. 17(1), 314 (2025). https://doi.org/10.1007/s40820-025-01826-w
L. Jiang, Y. Ding, L. Li, Y. Tang, P. Zhou et al., Cationic adsorption-induced microlevelling effect: a pathway to dendrite-free zinc anodes. Nano-Micro Lett. 17(1), 202 (2025). https://doi.org/10.1007/s40820-025-01709-0
Y. Dai, H. He, M. Ouyang, J. Chen, J. Lin et al., In-operando X-ray imaging for sobering examination of aqueous zinc metal batteries. Nano-Micro Letters 18(1), 85 (2025). https://doi.org/10.1007/s40820-025-01911-0
M. Kim, J. Lee, Y. Kim, Y. Park, H. Kim et al., Surface overpotential as a key metric for the discharge–charge reversibility of aqueous zinc-ion batteries. J. Am. Chem. Soc. 145(29), 15776–15787 (2023). https://doi.org/10.1021/jacs.3c01614
S.S. Hemdan, A.M.A.L. Gebali, F.K. Ali, The electrostatic and non-electrostatic interaction affect on acidity constants of bromocresol purple in aqueous ethanolic media. J. Solution Chem. 53(6), 761–772 (2024). https://doi.org/10.1007/s10953-023-01270-7
N. Kari, S. Koxmak, K. Wumaier, P. Nizamidin, S. Abliz et al., Application of bromocresol purple nanofilm and laser light to detect mutton freshness. Spectrochim. Acta A Mol. Biomol. Spectrosc. 244, 118863 (2021). https://doi.org/10.1016/j.saa.2020.118863
I.M. Steinberg, A. Lobnik, O.S. Wolfbeis, Characterisation of an optical sensor membrane based on the metal ion indicator Pyrocatechol Violet. Sens. Actuators B Chem. 90(1–3), 230–235 (2003). https://doi.org/10.1016/S0925-4005(03)00033-9
H. Gan, H. Li, M. Xu, C. Han, H.-M. Cheng, Failure mechanisms and remedy of an ultrathin Zn metal anode in pouch cells. Joule 8(11), 3054–3071 (2024). https://doi.org/10.1016/j.joule.2024.07.013
T. Yan, B. Wu, S. Liu, M. Tao, J. Liang et al., Sieving-type electric double layer with hydrogen bond interlocking to stable zinc metal anode. Angew. Chem. Int. Ed. 63(47), e202411470 (2024). https://doi.org/10.1002/anie.202411470
J. Zhou, F. Wu, Y. Mei, Y. Hao, L. Li et al., Establishing thermal infusion method for stable zinc metal anodes in aqueous zinc-ion batteries. Adv. Mater. 34(21), 2200782 (2022). https://doi.org/10.1002/adma.202200782
H.P. de Oliveira, Determination of pKa of dyes by electrical impedance spectroscopy. Microchem. J. 88(1), 32–37 (2008). https://doi.org/10.1016/j.microc.2007.09.002
E. Hudson-Heck, X. Liu, R.H. Byrne, Purification and physical-chemical characterization of bromocresol purple for carbon system measurements in freshwaters, estuaries, and oceans. ACS Omega 6(28), 17941–17951 (2021). https://doi.org/10.1021/acsomega.1c01579
X. Sun, X. Zhang, K. Wang, Y. An, X. Zhang et al., Determination strategy of stable electrochemical operating voltage window for practical lithium-ion capacitors. Electrochim. Acta 428, 140972 (2022). https://doi.org/10.1016/j.electacta.2022.140972
K. Xu, S.P. Ding, T.R. Jow, Toward reliable values of electrochemical stability limits for electrolytes. J. Electrochem. Soc. 146(11), 4172–4178 (1999). https://doi.org/10.1149/1.1392609
D. Weingarth, H. Noh, A. Foelske-Schmitz, A. Wokaun, R. Kötz, A reliable determination method of stability limits for electrochemical double layer capacitors. Electrochim. Acta 103, 119–124 (2013). https://doi.org/10.1016/j.electacta.2013.04.057
C. Ding, T. Huang, Y. Tao, D. Tan, Y. Zhang et al., Identifying the origin and contribution of pseudocapacitive sodium ion storage in tungsten disulphide nanosheets for application in sodium-ion capacitors. J. Mater. Chem. A 6(42), 21010–21017 (2018). https://doi.org/10.1039/C8TA07677D
W. Fan, L. Qin, S. Alshammari, M.H. Helal, Z.M. El-Bahy et al., Opportunities for aqueous electrolytic zinc–manganese batteries. ACS Energy Lett. 10(8), 3914–3921 (2025). https://doi.org/10.1021/acsenergylett.5c01631
W. Fan, L. Qin, T.F. Altamimi, Z.M. El-Bahy, B. Lu et al., Redox mediators for aqueous electrolytic zinc-manganese batteries: fundamentals and design criteria. Adv. Energy Mater. 16(2), e04251 (2026). https://doi.org/10.1002/aenm.202504251
S.-E. Chun, B. Evanko, X. Wang, D. Vonlanthen, X. Ji et al., Design of aqueous redox-enhanced electrochemical capacitors with high specific energies and slow self-discharge. Nat. Commun. 6, 7818 (2015). https://doi.org/10.1038/ncomms8818
G. Shul, D. Bélanger, Self-discharge of electrochemical capacitors based on soluble or grafted quinone. Phys. Chem. Chem. Phys. 18(28), 19137–19145 (2016). https://doi.org/10.1039/c6cp02356h
C. Cougnon, Exploring the interdependence between the coulombic, voltage and energy efficiencies. Electrochem. Commun. 120, 106832 (2020). https://doi.org/10.1016/j.elecom.2020.106832
M.C.G. Santos, G.G. Silva, R. Santamaría, P.F.R. Ortega, R.L. Lavall, Discussion on operational voltage and efficiencies of ionic-liquid-based electrochemical capacitors. J. Phys. Chem. C 123(14), 8541–8549 (2019). https://doi.org/10.1021/acs.jpcc.8b11607