Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode

Sodium-ion batteries are attractive energy storage media owing to the abundance of sodium, but the low capacities of available cathode materials make them impractical. Sodium-excess metal oxides Na(2)MO(3) (M: transition metal) are appealing cathode materials that may realize large capacities throug...

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Autores principales: Mortemard de Boisse, Benoit, Liu, Guandong, Ma, Jiangtao, Nishimura, Shin-ichi, Chung, Sai-Cheong, Kiuchi, Hisao, Harada, Yoshihisa, Kikkawa, Jun, Kobayashi, Yoshio, Okubo, Masashi, Yamada, Atsuo
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group 2016
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Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4837481/
https://www.ncbi.nlm.nih.gov/pubmed/27088834
http://dx.doi.org/10.1038/ncomms11397
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author Mortemard de Boisse, Benoit
Liu, Guandong
Ma, Jiangtao
Nishimura, Shin-ichi
Chung, Sai-Cheong
Kiuchi, Hisao
Harada, Yoshihisa
Kikkawa, Jun
Kobayashi, Yoshio
Okubo, Masashi
Yamada, Atsuo
author_facet Mortemard de Boisse, Benoit
Liu, Guandong
Ma, Jiangtao
Nishimura, Shin-ichi
Chung, Sai-Cheong
Kiuchi, Hisao
Harada, Yoshihisa
Kikkawa, Jun
Kobayashi, Yoshio
Okubo, Masashi
Yamada, Atsuo
author_sort Mortemard de Boisse, Benoit
collection PubMed
description Sodium-ion batteries are attractive energy storage media owing to the abundance of sodium, but the low capacities of available cathode materials make them impractical. Sodium-excess metal oxides Na(2)MO(3) (M: transition metal) are appealing cathode materials that may realize large capacities through additional oxygen redox reaction. However, the general strategies for enhancing the capacity of Na(2)MO(3) are poorly established. Here using two polymorphs of Na(2)RuO(3), we demonstrate the critical role of honeycomb-type cation ordering in Na(2)MO(3). Ordered Na(2)RuO(3) with honeycomb-ordered [Na(1/3)Ru(2/3)]O(2) slabs delivers a capacity of 180 mAh g(−1) (1.3-electron reaction), whereas disordered Na(2)RuO(3) only delivers 135 mAh g(−1) (1.0-electron reaction). We clarify that the large extra capacity of ordered Na(2)RuO(3) is enabled by a spontaneously ordered intermediate Na(1)RuO(3) phase with ilmenite O1 structure, which induces frontier orbital reorganization to trigger the oxygen redox reaction, unveiling a general requisite for the stable oxygen redox reaction in high-capacity Na(2)MO(3) cathodes.
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spelling pubmed-48374812016-05-04 Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode Mortemard de Boisse, Benoit Liu, Guandong Ma, Jiangtao Nishimura, Shin-ichi Chung, Sai-Cheong Kiuchi, Hisao Harada, Yoshihisa Kikkawa, Jun Kobayashi, Yoshio Okubo, Masashi Yamada, Atsuo Nat Commun Article Sodium-ion batteries are attractive energy storage media owing to the abundance of sodium, but the low capacities of available cathode materials make them impractical. Sodium-excess metal oxides Na(2)MO(3) (M: transition metal) are appealing cathode materials that may realize large capacities through additional oxygen redox reaction. However, the general strategies for enhancing the capacity of Na(2)MO(3) are poorly established. Here using two polymorphs of Na(2)RuO(3), we demonstrate the critical role of honeycomb-type cation ordering in Na(2)MO(3). Ordered Na(2)RuO(3) with honeycomb-ordered [Na(1/3)Ru(2/3)]O(2) slabs delivers a capacity of 180 mAh g(−1) (1.3-electron reaction), whereas disordered Na(2)RuO(3) only delivers 135 mAh g(−1) (1.0-electron reaction). We clarify that the large extra capacity of ordered Na(2)RuO(3) is enabled by a spontaneously ordered intermediate Na(1)RuO(3) phase with ilmenite O1 structure, which induces frontier orbital reorganization to trigger the oxygen redox reaction, unveiling a general requisite for the stable oxygen redox reaction in high-capacity Na(2)MO(3) cathodes. Nature Publishing Group 2016-04-18 /pmc/articles/PMC4837481/ /pubmed/27088834 http://dx.doi.org/10.1038/ncomms11397 Text en Copyright © 2016, Nature Publishing Group, a division of Macmillan Publishers Limited. All Rights Reserved. http://creativecommons.org/licenses/by/4.0/ This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/
spellingShingle Article
Mortemard de Boisse, Benoit
Liu, Guandong
Ma, Jiangtao
Nishimura, Shin-ichi
Chung, Sai-Cheong
Kiuchi, Hisao
Harada, Yoshihisa
Kikkawa, Jun
Kobayashi, Yoshio
Okubo, Masashi
Yamada, Atsuo
Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode
title Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode
title_full Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode
title_fullStr Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode
title_full_unstemmed Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode
title_short Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode
title_sort intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4837481/
https://www.ncbi.nlm.nih.gov/pubmed/27088834
http://dx.doi.org/10.1038/ncomms11397
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