Electrochemical behavior of electrolytic manganese dioxide in aqueous KOH and LiOH solutions: A comparative study

Eric D. Rus, Geon Dae Moon, Jianming Bai, Daniel Artemus Steingart, Can K. Erdonmez

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18 Scopus citations

Abstract

As an inexpensive and high capacity oxidant, electrolytic manganese dioxide (γ-MnO2) is of interest as a cathode for secondary aqueous batteries. Electrochemical behavior of γ-MnO2 was characterized in aqueous 5.0 M KOH and LiOH solutions, and found to depend strongly upon cation identity. In LiOH and mixed LiOH / KOH solutions, Li-ion intercalation appeared to operate in competition with proton intercalation, being favored at higher [Li+] and, for mixed electrolytes, lower sweep rates. Electrochemical and in situ X-ray diffraction data indicated that γ-MnO2 underwent a chemically irreversible transformation upon the first reduction in LiOH solution, while in KOH solution, structure was largely unchanged after the first cycle. These experiments with γ-MnO2 as well as with a closely-related, ramsdellite-like sample, suggest that depending on sample morphology/rate capability, the irreversible process proceeds either through a solid-solution reaction or a two-phase reaction followed by a solid-solution reaction. While discharge capacity and capacity retention during galvanostatic cycling of γ-MnO2 were worse in LiOH than in KOH solution, some improvement was noted in a mixed LiOH/KOH solution.

Original languageEnglish (US)
Pages (from-to)A356-A363
JournalJournal of the Electrochemical Society
Volume163
Issue number3
DOIs
StatePublished - Jan 1 2016

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Renewable Energy, Sustainability and the Environment
  • Surfaces, Coatings and Films
  • Electrochemistry
  • Materials Chemistry

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