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

Title
Critical Role of pH Evolution of Electrolyte in the Reaction Mechanism for Rechargeable Zinc Batteries
Authors
조병원오시형정경윤이보은서효리이해리윤증승김종학
Keywords
manganese dioxide; zinc; battery; mechanism; zinc hydroxide sulfate; pH
Issue Date
2016-10
Publisher
ChemSusChem
Citation
VOL 9-2956
Abstract
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  H2 O) 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
URI
http://pubs.kist.re.kr/handle/201004/64904
ISSN
1864-5631
Appears in Collections:
KIST Publication > Article
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