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Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi(0.8)Co(0.2−y)Al(y)O(2) Cathodes

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 combin...

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Autores principales: 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.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6881288/
https://www.ncbi.nlm.nih.gov/pubmed/31776363
http://dx.doi.org/10.1038/s41598-019-53932-6
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author 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.
author_facet 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.
author_sort Lebens-Higgins, Zachary W.
collection PubMed
description 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 LiNi(0.8)Co(0.2−y)AlyO(2) (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 LiPF(6) salt with the more thermally stable LiBF(4) 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 LiPF(6) (LiBF(4)). 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 LiPF(6) and LiBF(4), 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.
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spelling pubmed-68812882019-12-05 Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi(0.8)Co(0.2−y)Al(y)O(2) Cathodes 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. Sci Rep Article 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 LiNi(0.8)Co(0.2−y)AlyO(2) (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 LiPF(6) salt with the more thermally stable LiBF(4) 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 LiPF(6) (LiBF(4)). 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 LiPF(6) and LiBF(4), 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. Nature Publishing Group UK 2019-11-27 /pmc/articles/PMC6881288/ /pubmed/31776363 http://dx.doi.org/10.1038/s41598-019-53932-6 Text en © The Author(s) 2019 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.
spellingShingle Article
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 LiNi(0.8)Co(0.2−y)Al(y)O(2) Cathodes
title Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi(0.8)Co(0.2−y)Al(y)O(2) Cathodes
title_full Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi(0.8)Co(0.2−y)Al(y)O(2) Cathodes
title_fullStr Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi(0.8)Co(0.2−y)Al(y)O(2) Cathodes
title_full_unstemmed Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi(0.8)Co(0.2−y)Al(y)O(2) Cathodes
title_short Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi(0.8)Co(0.2−y)Al(y)O(2) Cathodes
title_sort surface chemistry dependence on aluminum doping in ni-rich lini(0.8)co(0.2−y)al(y)o(2) cathodes
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6881288/
https://www.ncbi.nlm.nih.gov/pubmed/31776363
http://dx.doi.org/10.1038/s41598-019-53932-6
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