--- _id: '7280' abstract: - lang: eng text: 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. article_number: '1380' article_processing_charge: No article_type: original author: - first_name: Won-Jin full_name: Kwak, Won-Jin last_name: Kwak - first_name: Hun full_name: Kim, Hun last_name: Kim - first_name: Yann K. full_name: Petit, Yann K. last_name: Petit - first_name: Christian full_name: Leypold, Christian last_name: Leypold - first_name: Trung Thien full_name: Nguyen, Trung Thien last_name: Nguyen - first_name: Nika full_name: Mahne, Nika last_name: Mahne - first_name: Paul full_name: Redfern, Paul last_name: Redfern - first_name: Larry A. full_name: Curtiss, Larry A. last_name: Curtiss - first_name: Hun-Gi full_name: Jung, Hun-Gi last_name: Jung - first_name: Sergey M. full_name: Borisov, Sergey M. last_name: Borisov - first_name: Stefan Alexander full_name: Freunberger, Stefan Alexander id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425 last_name: Freunberger orcid: 0000-0003-2902-5319 - first_name: Yang-Kook full_name: Sun, Yang-Kook last_name: Sun citation: ama: Kwak W-J, Kim H, Petit YK, et al. Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen. Nature Communications. 2019;10. doi:10.1038/s41467-019-09399-0 apa: 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. Springer Nature. https://doi.org/10.1038/s41467-019-09399-0 chicago: Kwak, Won-Jin, Hun Kim, Yann K. Petit, Christian Leypold, Trung Thien Nguyen, Nika Mahne, Paul Redfern, et al. “Deactivation of Redox Mediators in Lithium-Oxygen Batteries by Singlet Oxygen.” Nature Communications. Springer Nature, 2019. https://doi.org/10.1038/s41467-019-09399-0. ieee: W.-J. Kwak et al., “Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen,” Nature Communications, vol. 10. Springer Nature, 2019. ista: Kwak W-J, Kim H, Petit YK, Leypold C, Nguyen TT, Mahne N, Redfern P, Curtiss LA, Jung H-G, Borisov SM, Freunberger SA, Sun Y-K. 2019. Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen. Nature Communications. 10, 1380. mla: Kwak, Won-Jin, et al. “Deactivation of Redox Mediators in Lithium-Oxygen Batteries by Singlet Oxygen.” Nature Communications, vol. 10, 1380, Springer Nature, 2019, doi:10.1038/s41467-019-09399-0. short: W.-J. Kwak, H. Kim, Y.K. Petit, C. Leypold, T.T. Nguyen, N. Mahne, P. Redfern, L.A. Curtiss, H.-G. Jung, S.M. Borisov, S.A. Freunberger, Y.-K. Sun, Nature Communications 10 (2019). date_created: 2020-01-15T12:12:26Z date_published: 2019-03-26T00:00:00Z date_updated: 2021-01-12T08:12:44Z day: '26' ddc: - '540' doi: 10.1038/s41467-019-09399-0 extern: '1' file: - access_level: open_access checksum: 123dd33e7f26761c82c74e10811a1e4d content_type: application/pdf creator: dernst date_created: 2020-01-22T15:58:54Z date_updated: 2020-07-14T12:47:55Z file_id: '7355' file_name: 2019_NatureComm_Kwak.pdf file_size: 1003676 relation: main_file file_date_updated: 2020-07-14T12:47:55Z has_accepted_license: '1' intvolume: ' 10' language: - iso: eng license: https://creativecommons.org/licenses/by/4.0/ month: '03' oa: 1 oa_version: Published Version publication: Nature Communications publication_identifier: issn: - 2041-1723 publication_status: published publisher: Springer Nature quality_controlled: '1' status: public title: Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen tmp: image: /images/cc_by.png legal_code_url: https://creativecommons.org/licenses/by/4.0/legalcode name: Creative Commons Attribution 4.0 International Public License (CC-BY 4.0) short: CC BY (4.0) type: journal_article user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87 volume: 10 year: '2019' ...