Critical Role of pH Evolution of Electrolyte in the Reaction Mechanism for Rechargeable Zinc Batteries

Boeun Lee, Hyo Ree Seo, Hae Ri Lee, Chong Seung Yoon, Jong Hak Kim, Kyung Yoon Chung, Byung Won Cho, Si Hyoung Oh

Research output: Contribution to journalArticlepeer-review

289 Citations (Scopus)


The reaction mechanism of α-MnO2 having 2×2 tunnel structure with zinc ions in a zinc rechargeable battery, employing an aqueous zinc sulfate electrolyte, was investigated by in situ monitoring structural changes and water chemistry alterations during the reaction. Contrary to the conventional belief that zinc ions intercalate into the tunnels of α-MnO2, we reveal that they actually precipitate in the form of layered zinc hydroxide sulfate (Zn4(OH)6(SO4)⋅5 H2O) on the α-MnO2 surface. This precipitation occurs because unstable trivalent manganese disproportionates and is dissolved in the electrolyte during the discharge process, resulting in a gradual increase in the pH value of the electrolyte. This causes zinc hydroxide sulfate to crystallize from the electrolyte on the electrode surface. During the charge process, the pH value of the electrolyte decreases due to recombination of manganese on the cathode, leading to dissolution of zinc hydroxide sulfate back into the electrolyte. An analogous phenomenon is also observed in todorokite, a manganese dioxide polymorph with 3×3 tunnel structure that is an indication for the critical role of pH changes of the electrolyte in the reaction mechanism of this battery system.

Original languageEnglish
Pages (from-to)2948-2956
Number of pages9
Issue number20
Publication statusPublished - 2016 Oct 20

Bibliographical note

Publisher Copyright:
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

All Science Journal Classification (ASJC) codes

  • Environmental Chemistry
  • Chemical Engineering(all)
  • Materials Science(all)
  • Energy(all)


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