Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen

Mahne, Nika; Renfrew, Sara E.; McCloskey, Bryan D.; Freunberger, Stefan A.

doi:10.1002/anie.201802277

Title: Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen

Journal Article · 13 April 2018 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.201802277 · OSTI ID:1433266

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Institute for Chemistry and Technology of Materials Graz University of Technology Stremayrgasse 9 8010 Graz Austria
Energy Storage and Distributed Resources Division Lawrence Berkeley National Laboratory, Department of Chemical and Biomolecular Engineering University of California – Berkeley Berkeley CA 94720 USA

Abstract Solid alkali metal carbonates are universal passivation layer components of intercalation battery materials and common side products in metal‐O ₂ batteries, and are believed to form and decompose reversibly in metal‐O ₂ /CO ₂ cells. In these cathodes, Li ₂ CO ₃ decomposes to CO ₂ when exposed to potentials above 3.8 V vs. Li/Li ⁺ . However, O ₂ evolution, as would be expected according to the decomposition reaction 2 Li ₂ CO ₃ →4 Li ⁺ +4 e ⁻ +2 CO ₂ +O ₂ , 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 ( ¹ O ₂ ) forms upon oxidizing Li ₂ CO ₃ in an aprotic electrolyte and therefore does not evolve as O ₂ . These results have substantial implications for the long‐term cyclability of batteries: they underpin the importance of avoiding ¹ O ₂ in metal‐O ₂ batteries, question the possibility of a reversible metal‐O ₂ /CO ₂ battery based on a carbonate discharge product, and help explain the interfacial reactivity of transition‐metal cathodes with residual Li ₂ CO ₃ .

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Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; AC02-05CH11231

OSTI ID:: 1433266

Alternate ID(s):: OSTI ID: 1433267; OSTI ID: 1460317

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 19 Vol. 57; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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