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Title: Revealing of the Activation Pathway and Cathode Electrolyte Interphase Evolution of Li-Rich 0.5Li 2MnO 3·0.5LiNi 0.3Co 0.3Mn 0.4O 2 Cathode by in Situ Electrochemical Quartz Crystal Microbalance

Abstract

The first-cycle behavior of layered Li-rich oxides, including Li 2MnO 3 activation and cathode electrolyte interphase (CEI) formation, significantly influences their electrochemical performance. However, the Li 2MnO 3 activation pathway and the CEI formation process are still controversial. Here, the first-cycle properties of xLi 2MnO 3·(1- x) LiNi 0.3Co 0.3Mn 0.4O 2 ( x = 0, 0.5, 1) cathode materials were studied with an in situ electrochemical quartz crystal microbalance (EQCM). The results demonstrate that a synergistic effect between the layered Li 2MnO 3 and LiNi 0.3Co 0.3Mn 0.4O 2 structures can significantly affect the activation pathway of Li 1.2Ni 0.12Co 0.12Mn 0.56O 2, leading to an extra-high capacity. It is demonstrated that Li 2MnO 3 activation in Li-rich materials is dominated by electrochemical decomposition (oxygen redox), which is different from the activation process of pure Li 2MnO 3 governed by chemical decomposition (Li 2O evolution). CEI evolution is closely related to Li + extraction/insertion. Finally, the valence state variation of the metal ions (Ni, Co, Mn) in Li-rich materials can promote CEI formation. This study is of significance for understanding and designing Li-rich cathode-based batteries.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2];  [2];  [2]; ORCiD logo [3];  [2];  [4];  [2];  [3]; ORCiD logo [2]; ORCiD logo [5]; ORCiD logo [2]
  1. Xiamen Univ. (China); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Xiamen Univ. (China)
  3. Xiamen Univ. (China); Sichuan Univ., Chengdu (China)
  4. Southeast Univ., Nanjing (China); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; Natural Science Foundation of Fujian Province of China; China Scholarship Council
OSTI Identifier:
1619117
Grant/Contract Number:  
AC02-05CH11231; 21621091; 2015J01063; 201606310151
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 11; Journal Issue: 17; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
Li-rich materials; Li2MnO3 activation; oxygen redox; CEI evolution; in situ EQCM

Citation Formats

Yin, Zu-Wei, Peng, Xin-Xing, Li, Jun-Tao, Shen, Chong-Heng, Deng, Ya-Ping, Wu, Zhen-Guo, Zhang, Tao, Zhang, Qiu-Bo, Mo, Yu-Xue, Wang, Kai, Huang, Ling, Zheng, Haimei, and Sun, Shi-Gang. Revealing of the Activation Pathway and Cathode Electrolyte Interphase Evolution of Li-Rich 0.5Li2MnO3·0.5LiNi0.3Co0.3Mn0.4O2 Cathode by in Situ Electrochemical Quartz Crystal Microbalance. United States: N. p., 2019. Web. doi:10.1021/acsami.9b02236.
Yin, Zu-Wei, Peng, Xin-Xing, Li, Jun-Tao, Shen, Chong-Heng, Deng, Ya-Ping, Wu, Zhen-Guo, Zhang, Tao, Zhang, Qiu-Bo, Mo, Yu-Xue, Wang, Kai, Huang, Ling, Zheng, Haimei, & Sun, Shi-Gang. Revealing of the Activation Pathway and Cathode Electrolyte Interphase Evolution of Li-Rich 0.5Li2MnO3·0.5LiNi0.3Co0.3Mn0.4O2 Cathode by in Situ Electrochemical Quartz Crystal Microbalance. United States. doi:10.1021/acsami.9b02236.
Yin, Zu-Wei, Peng, Xin-Xing, Li, Jun-Tao, Shen, Chong-Heng, Deng, Ya-Ping, Wu, Zhen-Guo, Zhang, Tao, Zhang, Qiu-Bo, Mo, Yu-Xue, Wang, Kai, Huang, Ling, Zheng, Haimei, and Sun, Shi-Gang. Fri . "Revealing of the Activation Pathway and Cathode Electrolyte Interphase Evolution of Li-Rich 0.5Li2MnO3·0.5LiNi0.3Co0.3Mn0.4O2 Cathode by in Situ Electrochemical Quartz Crystal Microbalance". United States. doi:10.1021/acsami.9b02236. https://www.osti.gov/servlets/purl/1619117.
@article{osti_1619117,
title = {Revealing of the Activation Pathway and Cathode Electrolyte Interphase Evolution of Li-Rich 0.5Li2MnO3·0.5LiNi0.3Co0.3Mn0.4O2 Cathode by in Situ Electrochemical Quartz Crystal Microbalance},
author = {Yin, Zu-Wei and Peng, Xin-Xing and Li, Jun-Tao and Shen, Chong-Heng and Deng, Ya-Ping and Wu, Zhen-Guo and Zhang, Tao and Zhang, Qiu-Bo and Mo, Yu-Xue and Wang, Kai and Huang, Ling and Zheng, Haimei and Sun, Shi-Gang},
abstractNote = {The first-cycle behavior of layered Li-rich oxides, including Li2MnO3 activation and cathode electrolyte interphase (CEI) formation, significantly influences their electrochemical performance. However, the Li2MnO3 activation pathway and the CEI formation process are still controversial. Here, the first-cycle properties of xLi2MnO3·(1- x) LiNi0.3Co0.3Mn0.4O2 ( x = 0, 0.5, 1) cathode materials were studied with an in situ electrochemical quartz crystal microbalance (EQCM). The results demonstrate that a synergistic effect between the layered Li2MnO3 and LiNi0.3Co0.3Mn0.4O2 structures can significantly affect the activation pathway of Li1.2Ni0.12Co0.12Mn0.56O2, leading to an extra-high capacity. It is demonstrated that Li2MnO3 activation in Li-rich materials is dominated by electrochemical decomposition (oxygen redox), which is different from the activation process of pure Li2MnO3 governed by chemical decomposition (Li2O evolution). CEI evolution is closely related to Li+ extraction/insertion. Finally, the valence state variation of the metal ions (Ni, Co, Mn) in Li-rich materials can promote CEI formation. This study is of significance for understanding and designing Li-rich cathode-based batteries.},
doi = {10.1021/acsami.9b02236},
journal = {ACS Applied Materials and Interfaces},
issn = {1944-8244},
number = 17,
volume = 11,
place = {United States},
year = {2019},
month = {4}
}

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