Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen
[1];
[2];
[2];
[1]
- 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 .
- Research Organization:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Organization:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- Grant/Contract Number:
- 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) Vol. 57 Journal Issue: 19; ISSN 1433-7851
- Publisher:
- Wiley Blackwell (John Wiley & Sons)Copyright Statement
- Country of Publication:
- Germany
- Language:
- English
Web of Science
Similar Records
Targeted masking enables stable cycling of LiNi0.6Co0.2Mn0.2O2 at 4.6V
Atomic-scale constituting stable interface for improved LiNi0.6Mn0.2Co0.2O2 cathodes of lithium-ion batteries