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Cation Vacancies in MnO2 and Their Influence on Electrochemical Reactivity
Abstract
Two types of protons must be distinguished in the cation‐deficient ( γ ‐ or ε ‐ ) MnO 2 lattice: localized (Ruetschi) protons, associated with vacancies, and mobile (Coleman) protons, associated with electrons forming Mn 3+ ions. The localized protons provide “proton bridges” for chain‐type proton transfer. Thermogravimetric experiments reveal that the cation vacancy fraction remains invariant during proton (plus electron) insertion and that the cation‐deficient lattice becomes increasingly unstable with increasing degree of (topotactical) reduction. The activation energy of proton (plus electron) diffusion is of similar magnitude as the activation energy of electronic conductivity, while the activation energy of cation (vacancy) diffusion is several times larger.
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Citations
Cited by
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The critical role of point defects in improving the specific capacitance of δ-MnO2 nanosheets
Gao, P., Metz, P., Hey, T., Gong, Y., Liu, D., Edwards, D. D., Howe, J. Y., Huang, R., & Misture, S. T. (2017) · Nature Communications · doi:10.1038/ncomms14559 · Cited by 294
Metadata
- Authors
- Ruetschi, P., & Giovanoli, R.
- Venue
- Journal of The Electrochemical Society
- Publisher
- The Electrochemical Society
- Published
- 1988-11-01
- Volume
- 135
- Issue
- 11
- Pages
- 2663-2669
- ISSN
- 0013-4651 (ISSN-L)
- 1945-7111
- OpenAlex
- W2097224253
- Cited by
- 247
- References
- 0
- FWCI
- 2.42
- Type
- journal article
- Language
- en
- Open access
- closed
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