Copper activated near-full two-electron Mn4+/Mn2+ redox for mild aqueous Zn/MnO2 battery

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Original languageEnglish
Article number137923
Number of pages11
Journal / PublicationChemical Engineering Journal
Issue numberPart 1
Online published8 Jul 2022
Publication statusPublished - 15 Dec 2022


Compared with traditional one-electron Mn4+/Mn3+ redox couple (308 mAh g-1), two-electron Mn4+/Mn2+ redox mechanism doubles the theoretical capacity (616 mAh g-1) of Zn/MnO2 batteries. However, in most cases, activating the Mn4+/Mn2+ redox couple requires a low pH value, which often leads to corrosion issues. Herein, a binder-free Cu-doped ε-MnO2 (CMO) was synthesized through a facile electrodeposition method and the two-electron Mn4+/Mn2+ redox is achieved in near-neutral ZnSO4 electrolyte with a working potential window of 0.8–1.9 V. Detailed characterizations demonstrate that the synergistic effect between Cu and Mn can boost the further reduction of Mn4+ and Mn3+ to dissoluble Mn2+ below 1.1 V. Compared with the capacity of ε-MnO(MO, 282.4 mAh g-1), which mainly involves Mn4+/Mn3+ redox couple, the CMO cathode demonstrates an improved specific capacity of 397.4 mAh g-1 at 0.2 A g-1. Besides, the fast reaction kinetics of H+ insertion, Mn dissolution, and Mn deposition reactions endow CMO with excellent rate performance, achieving a high specific capacity of 298.9 mAh g-1 at 5 A g-1.

Research Area(s)

  • Two-electron transfer, Mn4+/Mn2+ redox, Mild electrolyte, Zn/MnO2 battery