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Title: Effect of Lithium Borate Additives on Cathode Film Formation in LiNi 0.5Mn 1.5O 4/Li Cells

A direct comparison of the cathode–electrolyte interface (CEI) generated on high-voltage LiNi 0.5Mn 1.5O 4 cathodes with three different lithium borate electrolyte additives, lithium bis(oxalato)borate (LiBOB), lithium 4-pyridyl trimethyl borate (LPTB), and lithium catechol dimethyl borate (LiCDMB), has been conducted. The lithium borate electrolyte additives have been previously reported to improve the capacity retention and efficiency of graphite/LiNi 0.5Mn 1.5O 4 cells due to the formation of passivating CEI. Linear sweep voltammetry (LSV) suggests that incorporation of the lithium borates into 1.2 M LiPF 6 in EC/EMC (3/7) electrolyte results in borate oxidation on the cathode surface at high potential. The reaction of the borates on the cathode surface leads to an increase in impedance as determined by electrochemical impedance spectroscopy (EIS), consistent with the formation of a cathode surface film. Ex-situ surface analysis of the electrode via a combination of SEM, TEM, IR-ATR, XPS, and high energy XPS (HAXPES) suggests that oxidation of all borate additives results in deposition of a passivation layer on the surface of LiNi 0.5Mn 1.5O 4 which inhibits transition metal ion dissolution from the cathode. The passivation layer thickness increases as a function of additive structure LiCDMB > LPTB > LiBOB. The results suggestmore » that the CEI thickness can be controlled by the structure and reactivity of the electrolyte additive.« less
Authors:
 [1] ; ORCiD logo [2] ;  [1] ;  [1] ;  [3] ;  [4] ; ORCiD logo [1]
  1. Univ. of Rhode Island, Kingston, RI (United States). Dept. of Chemistry
  2. Rhode Island College, Providence, RI (United States). Dept. of Physical Sciences
  3. Univ. of Rhode Island, Kingston, RI (United States). Dept. of Physics
  4. Canadian Light Sources, Inc., Saskatoon, SK (Canada)
Publication Date:
Grant/Contract Number:
SC0007074
Type:
Published Article
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 9; Journal Issue: 24; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Research Org:
Univ. of Rhode Island, Kingston, RI (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE; lithium ion battery; electrolyte; additive; cathode−electrolyte interface (CEI); high energy XPS (HAXPES)
OSTI Identifier:
1364664
Alternate Identifier(s):
OSTI ID: 1473878

Dong, Yingnan, Young, Benjamin T., Zhang, Yuzi, Yoon, Taeho, Heskett, David R., Hu, Yongfeng, and Lucht, Brett L.. Effect of Lithium Borate Additives on Cathode Film Formation in LiNi 0.5Mn1.5O4/Li Cells. United States: N. p., Web. doi:10.1021/acsami.7b01481.
Dong, Yingnan, Young, Benjamin T., Zhang, Yuzi, Yoon, Taeho, Heskett, David R., Hu, Yongfeng, & Lucht, Brett L.. Effect of Lithium Borate Additives on Cathode Film Formation in LiNi 0.5Mn1.5O4/Li Cells. United States. doi:10.1021/acsami.7b01481.
Dong, Yingnan, Young, Benjamin T., Zhang, Yuzi, Yoon, Taeho, Heskett, David R., Hu, Yongfeng, and Lucht, Brett L.. 2017. "Effect of Lithium Borate Additives on Cathode Film Formation in LiNi 0.5Mn1.5O4/Li Cells". United States. doi:10.1021/acsami.7b01481.
@article{osti_1364664,
title = {Effect of Lithium Borate Additives on Cathode Film Formation in LiNi 0.5Mn1.5O4/Li Cells},
author = {Dong, Yingnan and Young, Benjamin T. and Zhang, Yuzi and Yoon, Taeho and Heskett, David R. and Hu, Yongfeng and Lucht, Brett L.},
abstractNote = {A direct comparison of the cathode–electrolyte interface (CEI) generated on high-voltage LiNi 0.5Mn1.5O4 cathodes with three different lithium borate electrolyte additives, lithium bis(oxalato)borate (LiBOB), lithium 4-pyridyl trimethyl borate (LPTB), and lithium catechol dimethyl borate (LiCDMB), has been conducted. The lithium borate electrolyte additives have been previously reported to improve the capacity retention and efficiency of graphite/LiNi 0.5Mn1.5O4 cells due to the formation of passivating CEI. Linear sweep voltammetry (LSV) suggests that incorporation of the lithium borates into 1.2 M LiPF6 in EC/EMC (3/7) electrolyte results in borate oxidation on the cathode surface at high potential. The reaction of the borates on the cathode surface leads to an increase in impedance as determined by electrochemical impedance spectroscopy (EIS), consistent with the formation of a cathode surface film. Ex-situ surface analysis of the electrode via a combination of SEM, TEM, IR-ATR, XPS, and high energy XPS (HAXPES) suggests that oxidation of all borate additives results in deposition of a passivation layer on the surface of LiNi 0.5Mn1.5O4 which inhibits transition metal ion dissolution from the cathode. The passivation layer thickness increases as a function of additive structure LiCDMB > LPTB > LiBOB. The results suggest that the CEI thickness can be controlled by the structure and reactivity of the electrolyte additive.},
doi = {10.1021/acsami.7b01481},
journal = {ACS Applied Materials and Interfaces},
number = 24,
volume = 9,
place = {United States},
year = {2017},
month = {5}
}