Electrochemical oxidation of Lithium Carbonate generates singlet oxygen

N. Mahne, S.E. Renfrew, B.D. McCloskey, S.A. Freunberger, Angewandte Chemie International Edition 57 (2018) 5529–5533.

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Journal Article | Published | English
Author
Mahne, Nika; Renfrew, Sara E.; McCloskey, Bryan D.; Freunberger, Stefan AlexanderIST Austria
Abstract
Solid alkali metal carbonates are universal passivation layer components of intercalation battery materials and common side products in metal‐O2 batteries, and are believed to form and decompose reversibly in metal‐O2/CO2 cells. In these cathodes, Li2CO3 decomposes to CO2 when exposed to potentials above 3.8 V vs. Li/Li+. However, O2 evolution, as would be expected according to the decomposition reaction 2 Li2CO3→4 Li++4 e−+2 CO2+O2, is not detected. O atoms are thus unaccounted for, which was previously ascribed to unidentified parasitic reactions. Here, we show that highly reactive singlet oxygen (1O2) forms upon oxidizing Li2CO3 in an aprotic electrolyte and therefore does not evolve as O2. These results have substantial implications for the long‐term cyclability of batteries: they underpin the importance of avoiding 1O2 in metal‐O2 batteries, question the possibility of a reversible metal‐O2/CO2 battery based on a carbonate discharge product, and help explain the interfacial reactivity of transition‐metal cathodes with residual Li2CO3.
Publishing Year
Date Published
2018-03-15
Journal Title
Angewandte Chemie International Edition
Volume
57
Issue
19
Page
5529-5533
ISSN
IST-REx-ID

Cite this

Mahne N, Renfrew SE, McCloskey BD, Freunberger SA. Electrochemical oxidation of Lithium Carbonate generates singlet oxygen. Angewandte Chemie International Edition. 2018;57(19):5529-5533. doi:10.1002/anie.201802277
Mahne, N., Renfrew, S. E., McCloskey, B. D., & Freunberger, S. A. (2018). Electrochemical oxidation of Lithium Carbonate generates singlet oxygen. Angewandte Chemie International Edition, 57(19), 5529–5533. https://doi.org/10.1002/anie.201802277
Mahne, Nika, Sara E. Renfrew, Bryan D. McCloskey, and Stefan Alexander Freunberger. “Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen.” Angewandte Chemie International Edition 57, no. 19 (2018): 5529–33. https://doi.org/10.1002/anie.201802277.
N. Mahne, S. E. Renfrew, B. D. McCloskey, and S. A. Freunberger, “Electrochemical oxidation of Lithium Carbonate generates singlet oxygen,” Angewandte Chemie International Edition, vol. 57, no. 19, pp. 5529–5533, 2018.
Mahne N, Renfrew SE, McCloskey BD, Freunberger SA. 2018. Electrochemical oxidation of Lithium Carbonate generates singlet oxygen. Angewandte Chemie International Edition. 57(19), 5529–5533.
Mahne, Nika, et al. “Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen.” Angewandte Chemie International Edition, vol. 57, no. 19, Wiley, 2018, pp. 5529–33, doi:10.1002/anie.201802277.
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