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

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

doi:10.1038/s41467-019-09399-0

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

Journal Article · Tue Mar 26 00:00:00 EDT 2019 · Nature Communications

DOI:https://doi.org/10.1038/s41467-019-09399-0· OSTI ID:1505763

Kwak, Won -Jin ^[1]; Kim, Hun ^[1]; Petit, Yann K. ^[2]; Leypold, Christian ^[2]; Nguyen, Trung Thien ^[1]; Mahne, Nika ^[2]; Redfern, Paul ^[3]; Curtiss, Larry A. ^[3]; Jung, Hun -Gi ^[4]; Borisov, Sergey M. ^[2]; Freunberger, Stefan A. ^[2]; Sun, Yang -Kook ^[1]

Hanyang Univ., Seoul (Republic of Korea)
Graz Univ. of Technology, Graz (Austria)
Argonne National Lab. (ANL), Argonne, IL (United States)
Korea Inst. of Science and Technology, Seoul (Republic of Korea)

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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: Korea Institute of Energy Technology Evaluation and Planning (KETEP); National Research Foundation of Korea (NRF); European Research Council (ERC); Austrian Science Fund (FWF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1505763

Journal Information:: Nature Communications, Vol. 10, Issue 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 57 works

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