Proton enhanced dynamic battery chemistry for aprotic lithium-oxygen batteries.
Water contamination is generally considered to be detrimental to the performance of aprotic lithium-air batteries, whereas this view is challenged by recent contrasting observations. This has provoked a range of discussions on the role of water and its impact on batteries. In this work, a distinct battery chemistry that prevails in water-contaminated aprotic lithium-oxygen batteries is revealed. Both lithium ions and protons are found to be involved in the oxygen reduction and evolution reactions, and lithium hydroperoxide and lithium hydroxide are identified as predominant discharge products. The crystallographic and spectroscopic characteristics of lithium hydroperoxide monohydrate are scrutinized both experimentally and theoretically. Intriguingly, the reaction of lithium hydroperoxide with triiodide exhibits a faster kinetics, which enables a considerably lower overpotential during the charging process. The battery chemistry unveiled in this mechanistic study could provide important insights into the understanding of nominally aprotic lithium-oxygen batteries and help to tackle the critical issues confronted.
Department of Materials Science and Engineering, Faculty of Engineering, National University of Singapore, 117576 Singapore, Singapore.
Yun Guang
YG
Zhu
X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, USA.
Qi
Q
Liu
X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, USA.
Yangchun
Y
Rong
Department of Materials Science and Engineering, Faculty of Engineering, National University of Singapore, 117576 Singapore, Singapore.
Haomin
H
Chen
Department of Materials Science and Engineering, Faculty of Engineering, National University of Singapore, 117576 Singapore, Singapore.
Jing
J
Yang
Department of Materials Science and Engineering, Faculty of Engineering, National University of Singapore, 117576 Singapore, Singapore.
Chuankun
C
Jia
School of Chemistry and Biochemistry, The University of Western Australia, 35 Stirling Highway Crawley, Perth, Western Australia 6009, Australia.
Li-Juan
LJ
Yu
School of Chemistry and Biochemistry, The University of Western Australia, 35 Stirling Highway Crawley, Perth, Western Australia 6009, Australia.
Amir
A
Karton
X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, USA.
Yang
Y
Ren
Ningbo Institute of Material Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China.
Xiaoxiong
X
Xu
Department of Materials Science and Engineering, Faculty of Engineering, National University of Singapore, 117576 Singapore, Singapore.
Stefan
S
Adams
Department of Materials Science and Engineering, Faculty of Engineering, National University of Singapore, 117576 Singapore, Singapore.
Qing
Q
Wang