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Title: Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment

Abstract

Lithium-rich transition metal oxide (Li 1+XM 1–XO 2) cathodes have high energy density above 900 Wh kg –1 due to hybrid anion- and cation-redox (HACR) contributions, but critical issues such as oxygen release and voltage decay during cycling have prevented their application for years. Here we show that a molten molybdate-assisted LiO extraction at 700 °C creates lattice-coherent but depth (r)-dependent Li 1+X(r)M 1–X(r)O 2 particles with a Li-rich (X ≈ 0.2) interior, a Li-poor (X ≈ –0.05) surface and a continuous gradient in between. The gradient Li-rich single crystals eliminate the oxygen release to the electrolyte and, importantly, still allow stable oxygen redox contributions within. Here, both the metal valence states and the crystal structure are well maintained during cycling. The gradient HACR cathode displays a specific density of 843 Wh kg –1 after 200 cycles at 0.2C and 808 Wh kg –1 after 100 cycles at 1C, with very little oxygen release and consumption of electrolyte. This high-temperature immunization treatment can be generalized to leach other elements to avoid unexpected surface reactions in batteries.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [2]; ORCiD logo [1];  [2]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
OSTI Identifier:
1593263
Report Number(s):
BNL-213531-2020-JAAM
Journal ID: ISSN 2058-7546
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Nature Energy
Additional Journal Information:
Journal Volume: 4; Journal Issue: 12; Journal ID: ISSN 2058-7546
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Zhu, Zhi, Yu, Daiwei, Yang, Yang, Su, Cong, Huang, Yimeng, Dong, Yanhao, Waluyo, Iradwikanari, Wang, Baoming, Hunt, Adrian, Yao, Xiahui, Lee, Jinhyuk, Xue, Weijiang, and Li, Ju. Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment. United States: N. p., 2019. Web. doi:10.1038/s41560-019-0508-x.
Zhu, Zhi, Yu, Daiwei, Yang, Yang, Su, Cong, Huang, Yimeng, Dong, Yanhao, Waluyo, Iradwikanari, Wang, Baoming, Hunt, Adrian, Yao, Xiahui, Lee, Jinhyuk, Xue, Weijiang, & Li, Ju. Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment. United States. doi:10.1038/s41560-019-0508-x.
Zhu, Zhi, Yu, Daiwei, Yang, Yang, Su, Cong, Huang, Yimeng, Dong, Yanhao, Waluyo, Iradwikanari, Wang, Baoming, Hunt, Adrian, Yao, Xiahui, Lee, Jinhyuk, Xue, Weijiang, and Li, Ju. Thu . "Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment". United States. doi:10.1038/s41560-019-0508-x.
@article{osti_1593263,
title = {Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment},
author = {Zhu, Zhi and Yu, Daiwei and Yang, Yang and Su, Cong and Huang, Yimeng and Dong, Yanhao and Waluyo, Iradwikanari and Wang, Baoming and Hunt, Adrian and Yao, Xiahui and Lee, Jinhyuk and Xue, Weijiang and Li, Ju},
abstractNote = {Lithium-rich transition metal oxide (Li1+XM1–XO2) cathodes have high energy density above 900 Wh kg–1 due to hybrid anion- and cation-redox (HACR) contributions, but critical issues such as oxygen release and voltage decay during cycling have prevented their application for years. Here we show that a molten molybdate-assisted LiO extraction at 700 °C creates lattice-coherent but depth (r)-dependent Li1+X(r)M1–X(r)O2 particles with a Li-rich (X ≈ 0.2) interior, a Li-poor (X ≈ –0.05) surface and a continuous gradient in between. The gradient Li-rich single crystals eliminate the oxygen release to the electrolyte and, importantly, still allow stable oxygen redox contributions within. Here, both the metal valence states and the crystal structure are well maintained during cycling. The gradient HACR cathode displays a specific density of 843 Wh kg–1 after 200 cycles at 0.2C and 808 Wh kg–1 after 100 cycles at 1C, with very little oxygen release and consumption of electrolyte. This high-temperature immunization treatment can be generalized to leach other elements to avoid unexpected surface reactions in batteries.},
doi = {10.1038/s41560-019-0508-x},
journal = {Nature Energy},
number = 12,
volume = 4,
place = {United States},
year = {2019},
month = {12}
}

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