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Limitations of Ultrathin Al(2)O(3) Coatings on LNMO Cathodes

[Image: see text] This study demonstrates the application of Al(2)O(3) coatings for the high-voltage cathode material LiNi(0.5–x)Mn(1.5+x)O(4−δ) (LNMO) by atomic layer deposition. The ultrathin and uniform coatings (0.6–1.7 nm) were deposited on LNMO particles and characterized by scanning transmiss...

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Autores principales: Østli, Elise R., Tesfamhret, Yonas, Wenner, Sigurd, Lacey, Matthew J., Brandell, Daniel, Svensson, Ann Mari, Selbach, Sverre M., Wagner, Nils P.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8603187/
https://www.ncbi.nlm.nih.gov/pubmed/34805692
http://dx.doi.org/10.1021/acsomega.1c04457
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author Østli, Elise R.
Tesfamhret, Yonas
Wenner, Sigurd
Lacey, Matthew J.
Brandell, Daniel
Svensson, Ann Mari
Selbach, Sverre M.
Wagner, Nils P.
author_facet Østli, Elise R.
Tesfamhret, Yonas
Wenner, Sigurd
Lacey, Matthew J.
Brandell, Daniel
Svensson, Ann Mari
Selbach, Sverre M.
Wagner, Nils P.
author_sort Østli, Elise R.
collection PubMed
description [Image: see text] This study demonstrates the application of Al(2)O(3) coatings for the high-voltage cathode material LiNi(0.5–x)Mn(1.5+x)O(4−δ) (LNMO) by atomic layer deposition. The ultrathin and uniform coatings (0.6–1.7 nm) were deposited on LNMO particles and characterized by scanning transmission electron microscopy, inductively coupled plasma mass spectrometry, and X-ray photoelectron spectroscopy. Galvanostatic charge discharge cycling in half cells revealed, in contrast to many published studies, that even coatings of a thickness of 1 nm were detrimental to the cycling performance of LNMO. The complete coverage of the LNMO particles by the Al(2)O(3) coating can form a Li-ion diffusion barrier, which leads to high overpotentials and reduced reversible capacity. Several reports on Al(2)O(3)-coated LNMO using alternative coating methods, which would lead to a less homogeneous coating, revealed the superior electrochemical properties of the Al(2)O(3)-coated LNMO, suggesting that complete coverage of the particles might in fact be a disadvantage. We show that transition metal ion dissolution during prolonged cycling at 50 °C is not hindered by the coating, resulting in Ni and Mn deposits on the Li counter electrode. The Al(2)O(3)-coated LNMO particles showed severe signs of pitting dissolution, which may be attributed to HF attack caused by side reactions between the electrolyte and the Al(2)O(3) coating, which can lead to additional HF formation. The pitting dissolution was most severe for the thickest coating (1.7 nm). The uniform coating coverage may lead to non-uniform conduction paths for Li, where the active sites are more susceptible to HF attack. Few benefits of applications of very thin, uniform, and amorphous Al(2)O(3) coatings could thus be verified, and the coating is not offering long-term protection from HF attack.
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spelling pubmed-86031872021-11-19 Limitations of Ultrathin Al(2)O(3) Coatings on LNMO Cathodes Østli, Elise R. Tesfamhret, Yonas Wenner, Sigurd Lacey, Matthew J. Brandell, Daniel Svensson, Ann Mari Selbach, Sverre M. Wagner, Nils P. ACS Omega [Image: see text] This study demonstrates the application of Al(2)O(3) coatings for the high-voltage cathode material LiNi(0.5–x)Mn(1.5+x)O(4−δ) (LNMO) by atomic layer deposition. The ultrathin and uniform coatings (0.6–1.7 nm) were deposited on LNMO particles and characterized by scanning transmission electron microscopy, inductively coupled plasma mass spectrometry, and X-ray photoelectron spectroscopy. Galvanostatic charge discharge cycling in half cells revealed, in contrast to many published studies, that even coatings of a thickness of 1 nm were detrimental to the cycling performance of LNMO. The complete coverage of the LNMO particles by the Al(2)O(3) coating can form a Li-ion diffusion barrier, which leads to high overpotentials and reduced reversible capacity. Several reports on Al(2)O(3)-coated LNMO using alternative coating methods, which would lead to a less homogeneous coating, revealed the superior electrochemical properties of the Al(2)O(3)-coated LNMO, suggesting that complete coverage of the particles might in fact be a disadvantage. We show that transition metal ion dissolution during prolonged cycling at 50 °C is not hindered by the coating, resulting in Ni and Mn deposits on the Li counter electrode. The Al(2)O(3)-coated LNMO particles showed severe signs of pitting dissolution, which may be attributed to HF attack caused by side reactions between the electrolyte and the Al(2)O(3) coating, which can lead to additional HF formation. The pitting dissolution was most severe for the thickest coating (1.7 nm). The uniform coating coverage may lead to non-uniform conduction paths for Li, where the active sites are more susceptible to HF attack. Few benefits of applications of very thin, uniform, and amorphous Al(2)O(3) coatings could thus be verified, and the coating is not offering long-term protection from HF attack. American Chemical Society 2021-11-03 /pmc/articles/PMC8603187/ /pubmed/34805692 http://dx.doi.org/10.1021/acsomega.1c04457 Text en © 2021 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Østli, Elise R.
Tesfamhret, Yonas
Wenner, Sigurd
Lacey, Matthew J.
Brandell, Daniel
Svensson, Ann Mari
Selbach, Sverre M.
Wagner, Nils P.
Limitations of Ultrathin Al(2)O(3) Coatings on LNMO Cathodes
title Limitations of Ultrathin Al(2)O(3) Coatings on LNMO Cathodes
title_full Limitations of Ultrathin Al(2)O(3) Coatings on LNMO Cathodes
title_fullStr Limitations of Ultrathin Al(2)O(3) Coatings on LNMO Cathodes
title_full_unstemmed Limitations of Ultrathin Al(2)O(3) Coatings on LNMO Cathodes
title_short Limitations of Ultrathin Al(2)O(3) Coatings on LNMO Cathodes
title_sort limitations of ultrathin al(2)o(3) coatings on lnmo cathodes
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8603187/
https://www.ncbi.nlm.nih.gov/pubmed/34805692
http://dx.doi.org/10.1021/acsomega.1c04457
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