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Title: Proton enhanced dynamic battery chemistry for aprotic lithium–oxygen batteries

Abstract

Water is generally considered to be deteriorating to the performance of aprotic Li-air batteries, while it is challenged by the disparate effects observed recently. This has provoked a range of discussion on the role of water and its impact on the battery operation. In this work, a distinct battery chemistry that prevails in water-contaminated aprotic Li-O 2 batteries was discovered. Both lithium ions and protons were found to be involved in the oxygen reduction (ORR) and evolution reactions (OER), and LiOOH and LiOH were identified as predominant materials in the discharge product. As a new lithium compound, the crystallographic and spectroscopic characteristics of LiOOH∙H 2O were scrutinized both experimentally and theoretically. The structure of LiOOH∙H 2O was found to be closely related to that of LiOH∙H 2O implying a fast conversion kinetics between the two phases. Intriguingly, LiOOH∙H 2O exhibits superior dynamic property towards the reaction with I 3 -, which renders considerably lower overpotential during the charging process. We anticipate that the new battery chemistry unveiled in this mechanistic study would provide important insights to the understanding of nominally aprotic Li-O 2 batteries and help to tackle the critical issues confronted.

Authors:
 [1];  [2];  [2];  [1];  [1];  [1];  [3];  [3];  [2];  [4];  [1];  [1]
  1. National Univ. of Singapore (Singapore). Dept. of Materials Science and Engineering
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  3. Univ. of Western Australia, Perth, WA (Australia). School of Chemistry and Biochemistry
  4. Chinese Academy of Sciences (CAS), Ningbo (China). Ningbo Inst. of Material Technology and Engineering
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Singapore National Science Foundation; USDOE
OSTI Identifier:
1343120
Grant/Contract Number:
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Zhu, Yun Guang, Liu, Qi, Rong, Yangchun, Chen, Haomin, Yang, Jing, Jia, Chuankun, Yu, Li-Juan, Karton, Amir, Ren, Yang, Xu, Xiaoxiong, Adams, Stefan, and Wang, Qing. Proton enhanced dynamic battery chemistry for aprotic lithium–oxygen batteries. United States: N. p., 2017. Web. doi:10.1038/ncomms14308.
Zhu, Yun Guang, Liu, Qi, Rong, Yangchun, Chen, Haomin, Yang, Jing, Jia, Chuankun, Yu, Li-Juan, Karton, Amir, Ren, Yang, Xu, Xiaoxiong, Adams, Stefan, & Wang, Qing. Proton enhanced dynamic battery chemistry for aprotic lithium–oxygen batteries. United States. doi:10.1038/ncomms14308.
Zhu, Yun Guang, Liu, Qi, Rong, Yangchun, Chen, Haomin, Yang, Jing, Jia, Chuankun, Yu, Li-Juan, Karton, Amir, Ren, Yang, Xu, Xiaoxiong, Adams, Stefan, and Wang, Qing. Mon . "Proton enhanced dynamic battery chemistry for aprotic lithium–oxygen batteries". United States. doi:10.1038/ncomms14308. https://www.osti.gov/servlets/purl/1343120.
@article{osti_1343120,
title = {Proton enhanced dynamic battery chemistry for aprotic lithium–oxygen batteries},
author = {Zhu, Yun Guang and Liu, Qi and Rong, Yangchun and Chen, Haomin and Yang, Jing and Jia, Chuankun and Yu, Li-Juan and Karton, Amir and Ren, Yang and Xu, Xiaoxiong and Adams, Stefan and Wang, Qing},
abstractNote = {Water is generally considered to be deteriorating to the performance of aprotic Li-air batteries, while it is challenged by the disparate effects observed recently. This has provoked a range of discussion on the role of water and its impact on the battery operation. In this work, a distinct battery chemistry that prevails in water-contaminated aprotic Li-O2 batteries was discovered. Both lithium ions and protons were found to be involved in the oxygen reduction (ORR) and evolution reactions (OER), and LiOOH and LiOH were identified as predominant materials in the discharge product. As a new lithium compound, the crystallographic and spectroscopic characteristics of LiOOH∙H2O were scrutinized both experimentally and theoretically. The structure of LiOOH∙H2O was found to be closely related to that of LiOH∙H2O implying a fast conversion kinetics between the two phases. Intriguingly, LiOOH∙H2O exhibits superior dynamic property towards the reaction with I3-, which renders considerably lower overpotential during the charging process. We anticipate that the new battery chemistry unveiled in this mechanistic study would provide important insights to the understanding of nominally aprotic Li-O2 batteries and help to tackle the critical issues confronted.},
doi = {10.1038/ncomms14308},
journal = {Nature Communications},
number = ,
volume = 8,
place = {United States},
year = {Mon Feb 06 00:00:00 EST 2017},
month = {Mon Feb 06 00:00:00 EST 2017}
}

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Cited by: 13works
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  • The discharge and charge mechanisms of rechargeable Li-O-2 batteries have been the subject of extensive investigation recently. However, they are not fully understood yet. Here we report a systematic study of the morphological transition of Li2O2 from a single crystalline structure to a toroid like particle during the discharge-charge cycle, with the help of a theoretical model to explain the evolution of the Li2O2 at different stages of this process. The model suggests that the transition starts in the first monolayer of Li2O2, and is subsequently followed by a transition from particle growth to film growth if the applied currentmore » exceeds the exchange current for the oxygen reduction reaction in a Li-O-2 cell. Furthermore, a sustainable mass transport of the diffusive active species (e.g., O-2 and Li+) and evolution of the underlying interfaces are critical to dictate desirable oxygen reduction (discharge) and evolution (charge) reactions in the porous carbon electrode of a Li-O-2 cell.« less
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