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

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.

Authors:
 [1];  [1];  [2];  [2];  [1];  [2];  [3];  [3];  [4];  [2];  [2];  [1]
  1. Hanyang Univ., Seoul (Republic of Korea)
  2. Graz Univ. of Technology, Graz (Austria)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Korea Inst. of Science and Technology, Seoul (Republic of Korea)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
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)
OSTI Identifier:
1505763
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE

Citation Formats

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., and Sun, Yang -Kook. Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen. United States: N. p., 2019. Web. doi:10.1038/s41467-019-09399-0.
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. Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen. United States. doi:10.1038/s41467-019-09399-0.
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., and Sun, Yang -Kook. Tue . "Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen". United States. doi:10.1038/s41467-019-09399-0. https://www.osti.gov/servlets/purl/1505763.
@article{osti_1505763,
title = {Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen},
author = {Kwak, Won -Jin and Kim, Hun and Petit, Yann K. and Leypold, Christian and Nguyen, Trung Thien and Mahne, Nika and Redfern, Paul and Curtiss, Larry A. and Jung, Hun -Gi and Borisov, Sergey M. and Freunberger, Stefan A. and Sun, Yang -Kook},
abstractNote = {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.},
doi = {10.1038/s41467-019-09399-0},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {3}
}

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