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Title: Approaching the capacity limit of lithium cobalt oxide in lithium ion batteries via lanthanum and aluminium doping

Abstract

Here, lithium cobalt oxides (LiCoO 2) possess a high theoretical specific capacity of 274 mAh/g. However, cycling LiCoO 2-based batteries to voltages greater than 4.35 V vs. Li/Li + causes significant structural instability and severe capacity fade. Consequently, commercial LiCoO 2 exhibits a maximum capacity of only ~165 mAh/g. Here we develop a doping technique to tackle this long-standing issue of instability and thus increase the capacity of LiCoO 2. La and Al are concurrently doped into Co-containing precursors, followed by high-temperature calcination with lithium carbonate. The dopants are found to reside in the crystal lattice of LiCoO 2, where La works as a pillar to increase the c-axis distance and Al as a positively charged center, facilitating Li + diffusion, stabilizing the structure and suppressing the phase transition during cycling, even at a high cut-off voltage of 4.5 V. This doped LiCoO 2 displays an exceptionally high capacity of 190 mAh/g, cyclability with 96% capacity retention over 50 cycles and significantly enhanced rate capability.

Authors:
 [1];  [2];  [3];  [2];  [2];  [2]; ORCiD logo [2];  [2];  [2];  [2]; ORCiD logo [2]; ORCiD logo [2];  [2];  [2];  [3]
  1. Argonne National Lab. (ANL), Argonne, IL (United States); City Univ. of Hong Kong, Hong Kong (China)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Huawei Technologies, Shenzhen (China)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1487027
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Energy
Additional Journal Information:
Journal Volume: 3; Journal Issue: 11; Journal ID: ISSN 2058-7546
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Liu, Qi, Su, Xin, Lei, Dan, Qin, Yan, Wen, Jianguo, Guo, Fangmin, Wu, Yimin A., Rong, Yangchun, Kou, Ronghui, Xiao, Xianghui, Aguesse, Frederic, Bareño, Javier, Ren, Yang, Lu, Wenquan, and Li, Yangxing. Approaching the capacity limit of lithium cobalt oxide in lithium ion batteries via lanthanum and aluminium doping. United States: N. p., 2018. Web. doi:10.1038/s41560-018-0180-6.
Liu, Qi, Su, Xin, Lei, Dan, Qin, Yan, Wen, Jianguo, Guo, Fangmin, Wu, Yimin A., Rong, Yangchun, Kou, Ronghui, Xiao, Xianghui, Aguesse, Frederic, Bareño, Javier, Ren, Yang, Lu, Wenquan, & Li, Yangxing. Approaching the capacity limit of lithium cobalt oxide in lithium ion batteries via lanthanum and aluminium doping. United States. doi:10.1038/s41560-018-0180-6.
Liu, Qi, Su, Xin, Lei, Dan, Qin, Yan, Wen, Jianguo, Guo, Fangmin, Wu, Yimin A., Rong, Yangchun, Kou, Ronghui, Xiao, Xianghui, Aguesse, Frederic, Bareño, Javier, Ren, Yang, Lu, Wenquan, and Li, Yangxing. Mon . "Approaching the capacity limit of lithium cobalt oxide in lithium ion batteries via lanthanum and aluminium doping". United States. doi:10.1038/s41560-018-0180-6. https://www.osti.gov/servlets/purl/1487027.
@article{osti_1487027,
title = {Approaching the capacity limit of lithium cobalt oxide in lithium ion batteries via lanthanum and aluminium doping},
author = {Liu, Qi and Su, Xin and Lei, Dan and Qin, Yan and Wen, Jianguo and Guo, Fangmin and Wu, Yimin A. and Rong, Yangchun and Kou, Ronghui and Xiao, Xianghui and Aguesse, Frederic and Bareño, Javier and Ren, Yang and Lu, Wenquan and Li, Yangxing},
abstractNote = {Here, lithium cobalt oxides (LiCoO2) possess a high theoretical specific capacity of 274 mAh/g. However, cycling LiCoO2-based batteries to voltages greater than 4.35 V vs. Li/Li+ causes significant structural instability and severe capacity fade. Consequently, commercial LiCoO2 exhibits a maximum capacity of only ~165 mAh/g. Here we develop a doping technique to tackle this long-standing issue of instability and thus increase the capacity of LiCoO2. La and Al are concurrently doped into Co-containing precursors, followed by high-temperature calcination with lithium carbonate. The dopants are found to reside in the crystal lattice of LiCoO2, where La works as a pillar to increase the c-axis distance and Al as a positively charged center, facilitating Li+ diffusion, stabilizing the structure and suppressing the phase transition during cycling, even at a high cut-off voltage of 4.5 V. This doped LiCoO2 displays an exceptionally high capacity of 190 mAh/g, cyclability with 96% capacity retention over 50 cycles and significantly enhanced rate capability.},
doi = {10.1038/s41560-018-0180-6},
journal = {Nature Energy},
number = 11,
volume = 3,
place = {United States},
year = {2018},
month = {6}
}

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Figures / Tables:

Figure 1 Figure 1: Ex situ Characterization of D-LCO and P-LCO: (a) Schematic structures of doped CoCO3 and Co3O4, and the final product D-LCO; (b) The HRTEM image of D-LCO; (c)The HRXRD pattern of P-LCO; (d) The HRXRD pattern of D-LCO: λ=0.4593 Å; (e) Comparison of the (003) peak in P-LCO andmore » D-LCO; (f) Comparison of the characteristic peaks in the HRXRD patterns between 39.4° and 40.2°; (g) The SEM image of D-LCO.« less

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.