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Title: Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides

© 2017 The Author(s). Lithium-rich layered transition metal oxide positive electrodes offer access to anion redox at high potentials, thereby promising high energy densities for lithium-ion batteries. However, anion redox is also associated with several unfavorable electrochemical properties, such as open-circuit voltage hysteresis. Here we reveal that in Li 1.17-x Ni 0.21 Co 0.08 Mn 0.54 O 2 , these properties arise from a strong coupling between anion redox and cation migration. We combine various X-ray spectroscopic, microscopic, and structural probes to show that partially reversible transition metal migration decreases the potential of the bulk oxygen redox couple by > 1 V, leading to a reordering in the anionic and cationic redox potentials during cycling. First principles calculations show that this is due to the drastic change in the local oxygen coordination environments associated with the transition metal migration. We propose that this mechanism is involved in stabilizing the oxygen redox couple, which we observe spectroscopically to persist for 500 charge/discharge cycles.
Authors:
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Publication Date:
Grant/Contract Number:
AC02-05CH11231; AC02-76SF00515
Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Batteries; Solid-state chemistry
OSTI Identifier:
1417012
Alternate Identifier(s):
OSTI ID: 1416944

Gent, William E., Lim, Kipil, Liang, Yufeng, Li, Qinghao, Barnes, Taylor, Ahn, Sung-Jin, Stone, Kevin H., McIntire, Mitchell, Hong, Jihyun, Song, Jay Hyok, Li, Yiyang, Mehta, Apurva, Ermon, Stefano, Tyliszczak, Tolek, Kilcoyne, David, Vine, David, Park, Jin-Hwan, Doo, Seok-Kwang, Toney, Michael F., Yang, Wanli, Prendergast, David, and Chueh, William C.. Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides. United States: N. p., Web. doi:10.1038/s41467-017-02041-x.
Gent, William E., Lim, Kipil, Liang, Yufeng, Li, Qinghao, Barnes, Taylor, Ahn, Sung-Jin, Stone, Kevin H., McIntire, Mitchell, Hong, Jihyun, Song, Jay Hyok, Li, Yiyang, Mehta, Apurva, Ermon, Stefano, Tyliszczak, Tolek, Kilcoyne, David, Vine, David, Park, Jin-Hwan, Doo, Seok-Kwang, Toney, Michael F., Yang, Wanli, Prendergast, David, & Chueh, William C.. Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides. United States. doi:10.1038/s41467-017-02041-x.
Gent, William E., Lim, Kipil, Liang, Yufeng, Li, Qinghao, Barnes, Taylor, Ahn, Sung-Jin, Stone, Kevin H., McIntire, Mitchell, Hong, Jihyun, Song, Jay Hyok, Li, Yiyang, Mehta, Apurva, Ermon, Stefano, Tyliszczak, Tolek, Kilcoyne, David, Vine, David, Park, Jin-Hwan, Doo, Seok-Kwang, Toney, Michael F., Yang, Wanli, Prendergast, David, and Chueh, William C.. 2017. "Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides". United States. doi:10.1038/s41467-017-02041-x. https://www.osti.gov/servlets/purl/1417012.
@article{osti_1417012,
title = {Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides},
author = {Gent, William E. and Lim, Kipil and Liang, Yufeng and Li, Qinghao and Barnes, Taylor and Ahn, Sung-Jin and Stone, Kevin H. and McIntire, Mitchell and Hong, Jihyun and Song, Jay Hyok and Li, Yiyang and Mehta, Apurva and Ermon, Stefano and Tyliszczak, Tolek and Kilcoyne, David and Vine, David and Park, Jin-Hwan and Doo, Seok-Kwang and Toney, Michael F. and Yang, Wanli and Prendergast, David and Chueh, William C.},
abstractNote = {© 2017 The Author(s). Lithium-rich layered transition metal oxide positive electrodes offer access to anion redox at high potentials, thereby promising high energy densities for lithium-ion batteries. However, anion redox is also associated with several unfavorable electrochemical properties, such as open-circuit voltage hysteresis. Here we reveal that in Li 1.17-x Ni 0.21 Co 0.08 Mn 0.54 O 2 , these properties arise from a strong coupling between anion redox and cation migration. We combine various X-ray spectroscopic, microscopic, and structural probes to show that partially reversible transition metal migration decreases the potential of the bulk oxygen redox couple by > 1 V, leading to a reordering in the anionic and cationic redox potentials during cycling. First principles calculations show that this is due to the drastic change in the local oxygen coordination environments associated with the transition metal migration. We propose that this mechanism is involved in stabilizing the oxygen redox couple, which we observe spectroscopically to persist for 500 charge/discharge cycles.},
doi = {10.1038/s41467-017-02041-x},
journal = {Nature Communications},
number = 1,
volume = 8,
place = {United States},
year = {2017},
month = {12}
}

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