Effect of Lithium Borate Additives on Cathode Film Formation in LiNi0.5Mn1.5O4/Li Cells
Abstract
A direct comparison of the cathode–electrolyte interface (CEI) generated on high-voltage LiNi0.5Mn1.5O4 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/LiNi0.5Mn1.5O4 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 LiNi0.5Mn1.5O4 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 structuremore »
- Publication Date:
- Research Org.:
- Univ. of Rhode Island, Kingston, RI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1364664
- Alternate Identifier(s):
- OSTI ID: 1473878; OSTI ID: 1508297
- Grant/Contract Number:
- SC0007074
- Resource Type:
- Published Article
- Journal Name:
- ACS Applied Materials and Interfaces
- Additional Journal Information:
- Journal Name: ACS Applied Materials and Interfaces Journal Volume: 9 Journal Issue: 24; Journal ID: ISSN 1944-8244
- Publisher:
- American Chemical Society (ACS)
- 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); lithium ion battery, electrolyte, additive, cathode−electrolyte interface (CEI), high energy XPS (HAXPES)
Citation Formats
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 LiNi0.5Mn1.5O4/Li Cells. United States: N. p., 2017.
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 LiNi0.5Mn1.5O4/Li Cells. United States. https://doi.org/10.1021/acsami.7b01481
Dong, Yingnan, Young, Benjamin T., Zhang, Yuzi, Yoon, Taeho, Heskett, David R., Hu, Yongfeng, and Lucht, Brett L. Wed .
"Effect of Lithium Borate Additives on Cathode Film Formation in LiNi0.5Mn1.5O4/Li Cells". United States. https://doi.org/10.1021/acsami.7b01481.
@article{osti_1364664,
title = {Effect of Lithium Borate Additives on Cathode Film Formation in LiNi0.5Mn1.5O4/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 LiNi0.5Mn1.5O4 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/LiNi0.5Mn1.5O4 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 LiNi0.5Mn1.5O4 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 = {Wed May 31 00:00:00 EDT 2017},
month = {Wed May 31 00:00:00 EDT 2017}
}
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https://doi.org/10.1021/acsami.7b01481
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