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Strong Anionic Repulsion for Fast Na Kinetics in P2‐Type Layered Oxides

An intriguing mechanism for enabling fast Na kinetics during oxygen redox (OR) is proposed to produce high‐power‐density cathodes for sodium‐ion batteries (SIBs) based on the P2‐type oxide models, Na(2/3)[Mn(6/9)Ni(3/9)]O(2) (NMNO) and Na(2/3)[Ti(1/9)Mn(5/9)Ni(3/9)]O(2) (NTMNO) using the “potential...

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Autores principales: Kwon, Dohyeong, Park, Sung‐Joon, Lee, Jaewoon, Park, Sangeon, Yu, Seung‐Ho, Kim, Duho
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10074072/
https://www.ncbi.nlm.nih.gov/pubmed/36748280
http://dx.doi.org/10.1002/advs.202206367
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author Kwon, Dohyeong
Park, Sung‐Joon
Lee, Jaewoon
Park, Sangeon
Yu, Seung‐Ho
Kim, Duho
author_facet Kwon, Dohyeong
Park, Sung‐Joon
Lee, Jaewoon
Park, Sangeon
Yu, Seung‐Ho
Kim, Duho
author_sort Kwon, Dohyeong
collection PubMed
description An intriguing mechanism for enabling fast Na kinetics during oxygen redox (OR) is proposed to produce high‐power‐density cathodes for sodium‐ion batteries (SIBs) based on the P2‐type oxide models, Na(2/3)[Mn(6/9)Ni(3/9)]O(2) (NMNO) and Na(2/3)[Ti(1/9)Mn(5/9)Ni(3/9)]O(2) (NTMNO) using the “potential pillar” effect. The critical structural parameter of NTMNO lowers the Na migration barrier in the desodiated state because the electrostatic repulsion of O(2p)—O(2p) that occurs between transition metal layers is combined with the chemically stiff Ti(4+)(3d)—O(2p) bond to locally retain the strong repulsion effect. The NTMNO interlayer distance moderately decreases upon charging with oxygen oxidation, whereas that of NMNO decreases at a much faster rate, which can be explained by the dependence of OR activity on the coordination environment. Fundamental electrochemical experiments clearly indicate that the Ti doping of the bare material significantly improves its rate capability during OR, and detailed electrochemical and structural analyses show much faster Na kinetics for NTMNO than for NMNO. A systematic comparison of the two cathode oxides based on experiments and first‐principles calculations establishes the “potential pillar” concept of not only improving the sluggish Na kinetics upon OR reaction but also harnessing the full potential of the anionic redox for high‐power‐density SIBs.
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spelling pubmed-100740722023-04-06 Strong Anionic Repulsion for Fast Na Kinetics in P2‐Type Layered Oxides Kwon, Dohyeong Park, Sung‐Joon Lee, Jaewoon Park, Sangeon Yu, Seung‐Ho Kim, Duho Adv Sci (Weinh) Research Articles An intriguing mechanism for enabling fast Na kinetics during oxygen redox (OR) is proposed to produce high‐power‐density cathodes for sodium‐ion batteries (SIBs) based on the P2‐type oxide models, Na(2/3)[Mn(6/9)Ni(3/9)]O(2) (NMNO) and Na(2/3)[Ti(1/9)Mn(5/9)Ni(3/9)]O(2) (NTMNO) using the “potential pillar” effect. The critical structural parameter of NTMNO lowers the Na migration barrier in the desodiated state because the electrostatic repulsion of O(2p)—O(2p) that occurs between transition metal layers is combined with the chemically stiff Ti(4+)(3d)—O(2p) bond to locally retain the strong repulsion effect. The NTMNO interlayer distance moderately decreases upon charging with oxygen oxidation, whereas that of NMNO decreases at a much faster rate, which can be explained by the dependence of OR activity on the coordination environment. Fundamental electrochemical experiments clearly indicate that the Ti doping of the bare material significantly improves its rate capability during OR, and detailed electrochemical and structural analyses show much faster Na kinetics for NTMNO than for NMNO. A systematic comparison of the two cathode oxides based on experiments and first‐principles calculations establishes the “potential pillar” concept of not only improving the sluggish Na kinetics upon OR reaction but also harnessing the full potential of the anionic redox for high‐power‐density SIBs. John Wiley and Sons Inc. 2023-02-07 /pmc/articles/PMC10074072/ /pubmed/36748280 http://dx.doi.org/10.1002/advs.202206367 Text en © 2023 The Authors. Advanced Science published by Wiley‐VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Research Articles
Kwon, Dohyeong
Park, Sung‐Joon
Lee, Jaewoon
Park, Sangeon
Yu, Seung‐Ho
Kim, Duho
Strong Anionic Repulsion for Fast Na Kinetics in P2‐Type Layered Oxides
title Strong Anionic Repulsion for Fast Na Kinetics in P2‐Type Layered Oxides
title_full Strong Anionic Repulsion for Fast Na Kinetics in P2‐Type Layered Oxides
title_fullStr Strong Anionic Repulsion for Fast Na Kinetics in P2‐Type Layered Oxides
title_full_unstemmed Strong Anionic Repulsion for Fast Na Kinetics in P2‐Type Layered Oxides
title_short Strong Anionic Repulsion for Fast Na Kinetics in P2‐Type Layered Oxides
title_sort strong anionic repulsion for fast na kinetics in p2‐type layered oxides
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10074072/
https://www.ncbi.nlm.nih.gov/pubmed/36748280
http://dx.doi.org/10.1002/advs.202206367
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