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Title: Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi 0.5Mn 1.5O 4 Electrodes

The LiNi 0.5Mn 1.5O 4 spinel is an appealing cathode material for next generation rechargeable Li-ion batteries due to its high operating voltage of ~4.7 V (vs Li/Li +). Although it is widely believed that the full range of electrochemical cycling involves the redox of Ni(II)/(IV), it has not been experimentally clarified whether Ni(III) exists as the intermediate state or a double-electron transfer takes place. Here, combined with theoretical calculations, we show unambiguous spectroscopic evidence of the Ni(III) state when the LiNi 0.5Mn 1.5O 4 electrode is half charged. This provides a direct verification of single-electron-transfer reactions in LiNi 0.5Mn 1.5O 4 upon cycling, namely, from Ni(II) to Ni(III), then to Ni(IV). Additionally, by virtue of its surface sensitivity, soft X-ray absorption spectroscopy also reveals the electrochemically inactive Ni 2+ and Mn 2+ phases on the electrode surface. Our work provides the long-awaited clarification of the single-electron transfer mechanism in LiNi 0.5Mn 1.5O 4 electrodes. Furthermore, the experimental results serve as a benchmark for further spectroscopic characterizations of Ni-based battery electrodes.
Authors:
 [1] ;  [2] ;  [3] ;  [4] ;  [1] ;  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. New York Univ., New York, NY (United States)
  3. General Motors Global R&D Center, Warren, MI (United States)
  4. Optimal CAE Inc., Plymouth, MI (United States)
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 119; Journal Issue: 49; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; high voltage spinel; LiNi0.5Mn1.5O4; Ni(III); soft x-ray spectroscopy
OSTI Identifier:
1393001

Qiao, Ruimin, Wray, L. Andrew, Kim, Jung -Hyun, Pieczonka, Nicholas P. W., Harris, Stephen J., and Yang, Wanli. Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi0.5Mn1.5O4 Electrodes. United States: N. p., Web. doi:10.1021/acs.jpcc.5b07479.
Qiao, Ruimin, Wray, L. Andrew, Kim, Jung -Hyun, Pieczonka, Nicholas P. W., Harris, Stephen J., & Yang, Wanli. Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi0.5Mn1.5O4 Electrodes. United States. doi:10.1021/acs.jpcc.5b07479.
Qiao, Ruimin, Wray, L. Andrew, Kim, Jung -Hyun, Pieczonka, Nicholas P. W., Harris, Stephen J., and Yang, Wanli. 2015. "Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi0.5Mn1.5O4 Electrodes". United States. doi:10.1021/acs.jpcc.5b07479. https://www.osti.gov/servlets/purl/1393001.
@article{osti_1393001,
title = {Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi0.5Mn1.5O4 Electrodes},
author = {Qiao, Ruimin and Wray, L. Andrew and Kim, Jung -Hyun and Pieczonka, Nicholas P. W. and Harris, Stephen J. and Yang, Wanli},
abstractNote = {The LiNi0.5Mn1.5O4 spinel is an appealing cathode material for next generation rechargeable Li-ion batteries due to its high operating voltage of ~4.7 V (vs Li/Li+). Although it is widely believed that the full range of electrochemical cycling involves the redox of Ni(II)/(IV), it has not been experimentally clarified whether Ni(III) exists as the intermediate state or a double-electron transfer takes place. Here, combined with theoretical calculations, we show unambiguous spectroscopic evidence of the Ni(III) state when the LiNi0.5Mn1.5O4 electrode is half charged. This provides a direct verification of single-electron-transfer reactions in LiNi0.5Mn1.5O4 upon cycling, namely, from Ni(II) to Ni(III), then to Ni(IV). Additionally, by virtue of its surface sensitivity, soft X-ray absorption spectroscopy also reveals the electrochemically inactive Ni2+ and Mn2+ phases on the electrode surface. Our work provides the long-awaited clarification of the single-electron transfer mechanism in LiNi0.5Mn1.5O4 electrodes. Furthermore, the experimental results serve as a benchmark for further spectroscopic characterizations of Ni-based battery electrodes.},
doi = {10.1021/acs.jpcc.5b07479},
journal = {Journal of Physical Chemistry. C},
number = 49,
volume = 119,
place = {United States},
year = {2015},
month = {11}
}