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

Won-Jin Kwak, Hun Kim, Yann K. Petit, Christian Leypold, Trung Thien Nguyen, Nika Mahne, Paul Redfern, Larry A. Curtiss, Hun-Gi Jung, Sergey M. Borisov, Stefan A. Freunberger () and Yang-Kook Sun ()
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Won-Jin Kwak: Hanyang University
Hun Kim: Hanyang University
Yann K. Petit: Graz University of Technology
Christian Leypold: Graz University of Technology
Trung Thien Nguyen: Hanyang University
Nika Mahne: Graz University of Technology
Paul Redfern: Argonne National Laboratory
Larry A. Curtiss: Argonne National Laboratory
Hun-Gi Jung: Korea Institute of Science and Technology
Sergey M. Borisov: Graz University of Technology
Stefan A. Freunberger: Graz University of Technology
Yang-Kook Sun: Hanyang University

Nature Communications, 2019, vol. 10, issue 1, 1-8

Abstract: 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.

Date: 2019
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DOI: 10.1038/s41467-019-09399-0

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