Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi0.8Co0.2-yAlyO2 Cathodes
Abstract
Aluminum is a common dopant across oxide cathodes for improving the bulk and cathode-electrolyte interface (CEI) stability. Aluminum in the bulk is known to enhance structural and thermal stability, yet the exact influence of aluminum at the CEI remains unclear. To address this, we utilized a combination of X-ray photoelectron and absorption spectroscopy to identify aluminum surface environments and extent of transition metal reduction for Ni-rich LiNi0.8Co0.2-yAlyO2 (0%, 5%, or 20% Al) layered oxide cathodes tested at 4.75 V under thermal stress (60 °C). For these tests, we compared the conventional LiPF6 salt with the more thermally stable LiBF4 salt. The CEI layers are inherently different between these two electrolyte salts, particularly for the highest level of Al-doping (20%) where a thicker (thinner) CEI layer is found for LiPF6 (LiBF4). Focusing on the aluminum environment, we reveal the type of surface aluminum species are dependent on the electrolyte salt, as Al-O-F- and Al-F-like species form when using LiPF6 and LiBF4, respectively. In both cases, we find cathode-electrolyte reactions drive the formation of a protective Al-F-like barrier at the CEI in Al-doped oxide cathodes.
- Authors:
-
- Binghamton Univ., NY (United States)
- Univ. of Cambridge (United Kingdom)
- Rutgers Univ., North Brunswick, NJ (United States)
- Scienta Omicron AB, Uppsala (Sweden)
- Diamond Light Source Ltd., Oxfordshire (United Kingdom)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Binghamton Univ., NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- OSTI Identifier:
- 1591835
- Alternate Identifier(s):
- OSTI ID: 1596998
- Grant/Contract Number:
- AC02-05CH11231; SC0012583; DMR-1658990; DMR-1919704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Scientific Reports
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2045-2322
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; batteries; characterization and analytical techniques
Citation Formats
Lebens-Higgins, Zachary W., Halat, David M., Faenza, Nicholas V., Wahila, Matthew J., Mascheck, Manfred, Wiell, Tomas, Eriksson, Susanna K., Palmgren, Paul, Rodriguez, Jose, Badway, Fadwa, Pereira, Nathalie, Amatucci, Glenn G., Lee, Tien-Lin, Grey, Clare P., and Piper, Louis F. J. Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi0.8Co0.2-yAlyO2 Cathodes. United States: N. p., 2019.
Web. doi:10.1038/s41598-019-53932-6.
Lebens-Higgins, Zachary W., Halat, David M., Faenza, Nicholas V., Wahila, Matthew J., Mascheck, Manfred, Wiell, Tomas, Eriksson, Susanna K., Palmgren, Paul, Rodriguez, Jose, Badway, Fadwa, Pereira, Nathalie, Amatucci, Glenn G., Lee, Tien-Lin, Grey, Clare P., & Piper, Louis F. J. Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi0.8Co0.2-yAlyO2 Cathodes. United States. https://doi.org/10.1038/s41598-019-53932-6
Lebens-Higgins, Zachary W., Halat, David M., Faenza, Nicholas V., Wahila, Matthew J., Mascheck, Manfred, Wiell, Tomas, Eriksson, Susanna K., Palmgren, Paul, Rodriguez, Jose, Badway, Fadwa, Pereira, Nathalie, Amatucci, Glenn G., Lee, Tien-Lin, Grey, Clare P., and Piper, Louis F. J. Wed .
"Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi0.8Co0.2-yAlyO2 Cathodes". United States. https://doi.org/10.1038/s41598-019-53932-6. https://www.osti.gov/servlets/purl/1591835.
@article{osti_1591835,
title = {Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi0.8Co0.2-yAlyO2 Cathodes},
author = {Lebens-Higgins, Zachary W. and Halat, David M. and Faenza, Nicholas V. and Wahila, Matthew J. and Mascheck, Manfred and Wiell, Tomas and Eriksson, Susanna K. and Palmgren, Paul and Rodriguez, Jose and Badway, Fadwa and Pereira, Nathalie and Amatucci, Glenn G. and Lee, Tien-Lin and Grey, Clare P. and Piper, Louis F. J.},
abstractNote = {Aluminum is a common dopant across oxide cathodes for improving the bulk and cathode-electrolyte interface (CEI) stability. Aluminum in the bulk is known to enhance structural and thermal stability, yet the exact influence of aluminum at the CEI remains unclear. To address this, we utilized a combination of X-ray photoelectron and absorption spectroscopy to identify aluminum surface environments and extent of transition metal reduction for Ni-rich LiNi0.8Co0.2-yAlyO2 (0%, 5%, or 20% Al) layered oxide cathodes tested at 4.75 V under thermal stress (60 °C). For these tests, we compared the conventional LiPF6 salt with the more thermally stable LiBF4 salt. The CEI layers are inherently different between these two electrolyte salts, particularly for the highest level of Al-doping (20%) where a thicker (thinner) CEI layer is found for LiPF6 (LiBF4). Focusing on the aluminum environment, we reveal the type of surface aluminum species are dependent on the electrolyte salt, as Al-O-F- and Al-F-like species form when using LiPF6 and LiBF4, respectively. In both cases, we find cathode-electrolyte reactions drive the formation of a protective Al-F-like barrier at the CEI in Al-doped oxide cathodes.},
doi = {10.1038/s41598-019-53932-6},
journal = {Scientific Reports},
number = 1,
volume = 9,
place = {United States},
year = {2019},
month = {11}
}
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