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Electrochemical Behavior of Electrolytic Manganese Dioxide in Aqueous KOH and LiOH Solutions: A Comparative Study

Author(s): Rus, Eric D; Moon, Geon Dae; Bai, Jianming; Steingart, Daniel A; Erdonmez, Can K

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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.
Publication Date: 9-Dec-2015
Electronic Publication Date: 9-Dec-2015
Citation: Rus, Eric D., Geon Dae Moon, Jianming Bai, Daniel A. Steingart, and Can K. Erdonmez. "Electrochemical behavior of electrolytic manganese dioxide in aqueous KOH and LiOH solutions: a comparative study." Journal of the Electrochemical Society 163, no. 3 (2015): A356-A363. doi: 10.1149/2.1011602jes
DOI: doi:10.1149/2.1011602jes
ISSN: 0013-4651
EISSN: 1945-7111
Pages: A356 - A363
Type of Material: Journal Article
Journal/Proceeding Title: Journal of the Electrochemical Society
Version: Final published version. This is an open access article.

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