Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen

Nika Mahne, Sara Renfrew, Bryan McCloskey, Stefan Freunberger

Publikation: Beitrag in einer FachzeitschriftArtikelForschungBegutachtung

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.

Originalspracheenglisch
Seiten (von - bis)5529-5533
Seitenumfang5
FachzeitschriftAngewandte Chemie / International Edition
Jahrgang57
Ausgabenummer19
DOIs
PublikationsstatusVeröffentlicht - 4 Mai 2018

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Lithium Carbonate
Singlet Oxygen
Electrochemical oxidation
Carbonates
Lithium
Metals
Oxygen
Cathodes
Alkali Metals
Alkali metals
Intercalation
Passivation
Electrolytes
Transition metals
Decomposition
Atoms

Fields of Expertise

  • Advanced Materials Science

Dies zitieren

Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen. / Mahne, Nika; Renfrew, Sara; McCloskey, Bryan; Freunberger, Stefan.

in: Angewandte Chemie / International Edition , Jahrgang 57, Nr. 19, 04.05.2018, S. 5529-5533.

Publikation: Beitrag in einer FachzeitschriftArtikelForschungBegutachtung

Mahne, Nika ; Renfrew, Sara ; McCloskey, Bryan ; Freunberger, Stefan. / Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen. in: Angewandte Chemie / International Edition . 2018 ; Jahrgang 57, Nr. 19. S. 5529-5533.
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N2 - 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.

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