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Surface chemical heterogeneous distribution in over-lithiated Li(1+x)CoO(2) electrodes

In commercial Li-ion batteries, the internal short circuits or over-lithiation often cause structural transformation in electrodes and may lead to safety risks. Herein, we investigate the over-discharged mechanism of LiCoO(2)/graphite pouch cells, especially spatially resolving the morphological, su...

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Autores principales: Sun, Gang, Yu, Fu-Da, Lu, Mi, Zhu, Qingjun, Jiang, Yunshan, Mao, Yongzhi, McLeod, John A., Maley, Jason, Wang, Jian, Zhou, Jigang, Wang, Zhenbo
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9617898/
https://www.ncbi.nlm.nih.gov/pubmed/36309496
http://dx.doi.org/10.1038/s41467-022-34161-4
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author Sun, Gang
Yu, Fu-Da
Lu, Mi
Zhu, Qingjun
Jiang, Yunshan
Mao, Yongzhi
McLeod, John A.
Maley, Jason
Wang, Jian
Zhou, Jigang
Wang, Zhenbo
author_facet Sun, Gang
Yu, Fu-Da
Lu, Mi
Zhu, Qingjun
Jiang, Yunshan
Mao, Yongzhi
McLeod, John A.
Maley, Jason
Wang, Jian
Zhou, Jigang
Wang, Zhenbo
author_sort Sun, Gang
collection PubMed
description In commercial Li-ion batteries, the internal short circuits or over-lithiation often cause structural transformation in electrodes and may lead to safety risks. Herein, we investigate the over-discharged mechanism of LiCoO(2)/graphite pouch cells, especially spatially resolving the morphological, surface phase, and local electronic structure of LiCoO(2) electrode. With synchrotron-based X-ray techniques and Raman mapping, together with spectroscopy simulations, we demonstrate that over-lithiation reaction is a surface effect, accompanied by Co reduction and surface structure transformation to Li(2)CoO(2)/Co(3)O(4)/CoO/Li(2)O-like phases. This surface chemical distribution variation is relevant to the depth and exposed crystalline planes of LiCoO(2) particles, and the distribution of binder/conductive additives. Theoretical calculations confirm that Li(2)CoO(2)-phase has lower electronic/ionic conductivity than LiCoO(2)-phase, further revealing the critical effect of distribution of conductive additives on the surface chemical heterogeneity evolution. Our findings on such surface phenomena are non-trivial and highlight the capability of synchrotron-based X-ray techniques for studying the spatial chemical phase heterogeneity.
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spelling pubmed-96178982022-10-31 Surface chemical heterogeneous distribution in over-lithiated Li(1+x)CoO(2) electrodes Sun, Gang Yu, Fu-Da Lu, Mi Zhu, Qingjun Jiang, Yunshan Mao, Yongzhi McLeod, John A. Maley, Jason Wang, Jian Zhou, Jigang Wang, Zhenbo Nat Commun Article In commercial Li-ion batteries, the internal short circuits or over-lithiation often cause structural transformation in electrodes and may lead to safety risks. Herein, we investigate the over-discharged mechanism of LiCoO(2)/graphite pouch cells, especially spatially resolving the morphological, surface phase, and local electronic structure of LiCoO(2) electrode. With synchrotron-based X-ray techniques and Raman mapping, together with spectroscopy simulations, we demonstrate that over-lithiation reaction is a surface effect, accompanied by Co reduction and surface structure transformation to Li(2)CoO(2)/Co(3)O(4)/CoO/Li(2)O-like phases. This surface chemical distribution variation is relevant to the depth and exposed crystalline planes of LiCoO(2) particles, and the distribution of binder/conductive additives. Theoretical calculations confirm that Li(2)CoO(2)-phase has lower electronic/ionic conductivity than LiCoO(2)-phase, further revealing the critical effect of distribution of conductive additives on the surface chemical heterogeneity evolution. Our findings on such surface phenomena are non-trivial and highlight the capability of synchrotron-based X-ray techniques for studying the spatial chemical phase heterogeneity. Nature Publishing Group UK 2022-10-29 /pmc/articles/PMC9617898/ /pubmed/36309496 http://dx.doi.org/10.1038/s41467-022-34161-4 Text en © The Author(s) 2022 https://creativecommons.org/licenses/by/4.0/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/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Sun, Gang
Yu, Fu-Da
Lu, Mi
Zhu, Qingjun
Jiang, Yunshan
Mao, Yongzhi
McLeod, John A.
Maley, Jason
Wang, Jian
Zhou, Jigang
Wang, Zhenbo
Surface chemical heterogeneous distribution in over-lithiated Li(1+x)CoO(2) electrodes
title Surface chemical heterogeneous distribution in over-lithiated Li(1+x)CoO(2) electrodes
title_full Surface chemical heterogeneous distribution in over-lithiated Li(1+x)CoO(2) electrodes
title_fullStr Surface chemical heterogeneous distribution in over-lithiated Li(1+x)CoO(2) electrodes
title_full_unstemmed Surface chemical heterogeneous distribution in over-lithiated Li(1+x)CoO(2) electrodes
title_short Surface chemical heterogeneous distribution in over-lithiated Li(1+x)CoO(2) electrodes
title_sort surface chemical heterogeneous distribution in over-lithiated li(1+x)coo(2) electrodes
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9617898/
https://www.ncbi.nlm.nih.gov/pubmed/36309496
http://dx.doi.org/10.1038/s41467-022-34161-4
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