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Title: Trace doping of multiple elements enables stable battery cycling of LiCoO2 at 4.6 V

Abstract

LiCoO2 is a dominant cathode material for lithium-ion (Li-ion) batteries due to its high volumetric energy density, which could potentially be further improved by charging to high voltages. However, practical adoption of high-voltage charging is hindered by LiCoO2’s structural instability at the deeply delithiated state and the associated safety concerns. Here, we achieve stable cycling of LiCoO2 at 4.6 V (versus Li/Li+) through trace Ti–Mg–Al co-doping. Using state-of-the-art synchrotron X-ray imaging and spectroscopic techniques, we report the incorporation of Mg and Al into the LiCoO2 lattice, which inhibits the undesired phase transition at voltages above 4.5 V. We also show that, even in trace amounts, Ti segregates significantly at grain boundaries and on the surface, modifying the microstructure of the particles while stabilizing the surface oxygen at high voltages. These dopants contribute through different mechanisms and synergistically promote the cycle stability of LiCoO2 at 4.6 V.

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [1];  [4];  [4]; ORCiD logo [4]; ORCiD logo [5];  [6];  [7]; ORCiD logo [8];  [4]; ORCiD logo [6];  [9]; ORCiD logo [4];  [7];  [7]; ORCiD logo [1]
  1. Chinese Academy of Sciences (CAS), Beijing (China); Univ. of Chinese Academy of Sciences (CAS), Beijing (China)
  2. Chinese Academy of Sciences (CAS), Beijing (China); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  3. Jiangxi Normal Univ., Jiangxi (China)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States)
  5. Hunan Univ., Changsha (China)
  6. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  7. Chinese Academy of Sciences (CAS), Beijing (China)
  8. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  9. Beijing WeLion New Energy Technology, Beijing (China)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1529891
Alternate Identifier(s):
OSTI ID: 1594924; OSTI ID: 1661653
Report Number(s):
BNL-211815-2019-JAAM; BNL-219845-2020-JAAM
Journal ID: ISSN 2058-7546
Grant/Contract Number:  
SC0012704; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Nature Energy
Additional Journal Information:
Journal Volume: 4; Journal Issue: 7; Journal ID: ISSN 2058-7546
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE

Citation Formats

Zhang, Jie-Nan, Li, Qinghao, Ouyang, Chuying, Yu, Xiqian, Ge, Mingyuan, Huang, Xiaojing, Hu, Enyuan, Ma, Chao, Li, Shaofeng, Xiao, Ruijuan, Yang, Wanli, Chu, Yong, Liu, Yijin, Yu, Huigen, Yang, Xiao-Qing, Huang, Xuejie, Chen, Liquan, and Li, Hong. Trace doping of multiple elements enables stable battery cycling of LiCoO2 at 4.6 V. United States: N. p., 2019. Web. doi:10.1038/s41560-019-0409-z.
Zhang, Jie-Nan, Li, Qinghao, Ouyang, Chuying, Yu, Xiqian, Ge, Mingyuan, Huang, Xiaojing, Hu, Enyuan, Ma, Chao, Li, Shaofeng, Xiao, Ruijuan, Yang, Wanli, Chu, Yong, Liu, Yijin, Yu, Huigen, Yang, Xiao-Qing, Huang, Xuejie, Chen, Liquan, & Li, Hong. Trace doping of multiple elements enables stable battery cycling of LiCoO2 at 4.6 V. United States. doi:10.1038/s41560-019-0409-z.
Zhang, Jie-Nan, Li, Qinghao, Ouyang, Chuying, Yu, Xiqian, Ge, Mingyuan, Huang, Xiaojing, Hu, Enyuan, Ma, Chao, Li, Shaofeng, Xiao, Ruijuan, Yang, Wanli, Chu, Yong, Liu, Yijin, Yu, Huigen, Yang, Xiao-Qing, Huang, Xuejie, Chen, Liquan, and Li, Hong. Mon . "Trace doping of multiple elements enables stable battery cycling of LiCoO2 at 4.6 V". United States. doi:10.1038/s41560-019-0409-z. https://www.osti.gov/servlets/purl/1529891.
@article{osti_1529891,
title = {Trace doping of multiple elements enables stable battery cycling of LiCoO2 at 4.6 V},
author = {Zhang, Jie-Nan and Li, Qinghao and Ouyang, Chuying and Yu, Xiqian and Ge, Mingyuan and Huang, Xiaojing and Hu, Enyuan and Ma, Chao and Li, Shaofeng and Xiao, Ruijuan and Yang, Wanli and Chu, Yong and Liu, Yijin and Yu, Huigen and Yang, Xiao-Qing and Huang, Xuejie and Chen, Liquan and Li, Hong},
abstractNote = {LiCoO2 is a dominant cathode material for lithium-ion (Li-ion) batteries due to its high volumetric energy density, which could potentially be further improved by charging to high voltages. However, practical adoption of high-voltage charging is hindered by LiCoO2’s structural instability at the deeply delithiated state and the associated safety concerns. Here, we achieve stable cycling of LiCoO2 at 4.6 V (versus Li/Li+) through trace Ti–Mg–Al co-doping. Using state-of-the-art synchrotron X-ray imaging and spectroscopic techniques, we report the incorporation of Mg and Al into the LiCoO2 lattice, which inhibits the undesired phase transition at voltages above 4.5 V. We also show that, even in trace amounts, Ti segregates significantly at grain boundaries and on the surface, modifying the microstructure of the particles while stabilizing the surface oxygen at high voltages. These dopants contribute through different mechanisms and synergistically promote the cycle stability of LiCoO2 at 4.6 V.},
doi = {10.1038/s41560-019-0409-z},
journal = {Nature Energy},
number = 7,
volume = 4,
place = {United States},
year = {2019},
month = {6}
}

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