Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen

Won-Jin Kwak, Hun Kim, Yann Kevin Petit, Christian Leypold, Trung Thien Nguyen, Nika Mahne, Paul Redfern, Larry A. Curtiss, Hun-Gi Jung, Sergey Borisov, Stefan Freunberger, Yang-Kook Sun

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Non-aqueous lithium-oxygen batteries cycle by forming lithium peroxide during discharge and oxidizing it during recharge. The significant problem of oxidizing the solid insulating lithium peroxide can greatly be facilitated by incorporating redox mediators that shuttle electron-holes between the porous substrate and lithium peroxide. Redox mediator stability is thus key for energy efficiency, reversibility, and cycle life. However, the gradual deactivation of redox mediators during repeated cycling has not conclusively been explained. Here, we show that organic redox mediators are predominantly decomposed by singlet oxygen that forms during cycling. Their reaction with superoxide, previously assumed to mainly trigger their degradation, peroxide, and dioxygen, is orders of magnitude slower in comparison. The reduced form of the mediator is markedly more reactive towards singlet oxygen than the oxidized form, from which we derive reaction mechanisms supported by density functional theory calculations. Redox mediators must thus be designed for stability against singlet oxygen.

Original languageEnglish
Article number1380
Pages (from-to)1380
Number of pages8
JournalNature Communications
Volume10
Issue number1
DOIs
Publication statusPublished - 26 Mar 2019

Fingerprint

Singlet Oxygen
Lithium
deactivation
Oxidation-Reduction
Peroxides
electric batteries
peroxides
lithium
Oxygen
oxygen
cycles
inorganic peroxides
Life Cycle Stages
Superoxides
Density functional theory
Energy efficiency
Life cycle
actuators
Electrons
degradation

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Chemistry(all)
  • Biochemistry, Genetics and Molecular Biology(all)

Fields of Expertise

  • Advanced Materials Science

Cite this

Kwak, W-J., Kim, H., Petit, Y. K., Leypold, C., Nguyen, T. T., Mahne, N., ... Sun, Y-K. (2019). Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen. Nature Communications , 10(1), 1380. [1380]. https://doi.org/10.1038/s41467-019-09399-0

Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen. / Kwak, Won-Jin; Kim, Hun; Petit, Yann Kevin; Leypold, Christian; Nguyen, Trung Thien; Mahne, Nika; Redfern, Paul; Curtiss, Larry A.; Jung, Hun-Gi; Borisov, Sergey; Freunberger, Stefan; Sun, Yang-Kook.

In: Nature Communications , Vol. 10, No. 1, 1380, 26.03.2019, p. 1380.

Research output: Contribution to journalArticleResearchpeer-review

Kwak, W-J, Kim, H, Petit, YK, Leypold, C, Nguyen, TT, Mahne, N, Redfern, P, Curtiss, LA, Jung, H-G, Borisov, S, Freunberger, S & Sun, Y-K 2019, 'Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen' Nature Communications , vol. 10, no. 1, 1380, pp. 1380. https://doi.org/10.1038/s41467-019-09399-0
Kwak, Won-Jin ; Kim, Hun ; Petit, Yann Kevin ; Leypold, Christian ; Nguyen, Trung Thien ; Mahne, Nika ; Redfern, Paul ; Curtiss, Larry A. ; Jung, Hun-Gi ; Borisov, Sergey ; Freunberger, Stefan ; Sun, Yang-Kook. / Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen. In: Nature Communications . 2019 ; Vol. 10, No. 1. pp. 1380.
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