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Title: Anionic Redox Reaction-Induced High-Capacity and Low-Strain Cathode with Suppressed Phase Transition

Abstract

Layered metal oxides have attracted widespread attention as cathodes for Na-ion batteries (NIBs) because of easy synthesis, highly reversible Na de-intercalation/intercalation and high energy density. However, most reported layered oxides suffer from a complex phase transition upon a large amount of Na de-intercalation. Here we report a P2-type layered oxide cathode Na0.72[Li0.24Mn0.76]O2, which exhibits exceptionally high initial charge capacity of ~210 mAh/g (0.72 Na) based on a pure Anionic Redox Reaction (ARR). Surprisingly, it is found that the global P2 structure can be maintained with minimal volume change (1.35%) upon complete removal of Na+ ions. This is due to the reduced Columbic repulsion associated with ARR and consequent suppression of the phase transition as observed in other P2-materials. Here we reveal for the first time that ARR has the functionality of stabilizing the structure, in addition to its role of increasing the capacity which has already been known. This would pave the way for the further improvement of high-energy-density NIBs.

Authors:
; ; ; ; ; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1600597
Alternate Identifier(s):
OSTI ID: 1477970; OSTI ID: 1482326
Report Number(s):
BNL-209182-2018-JAAM; BNL-209445-2018-JAAM
Journal ID: ISSN 2542-4351; S2542435118305130; PII: S2542435118305130
Grant/Contract Number:  
SC0012704; AC02-06CH11357; AC05-00OR22725; AC02-05CH11231
Resource Type:
Journal Article: Published Article
Journal Name:
Joule
Additional Journal Information:
Journal Name: Joule Journal Volume: 3 Journal Issue: 2; Journal ID: ISSN 2542-4351
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Rong, Xiaohui, Hu, Enyuan, Lu, Yaxiang, Meng, Fanqi, Zhao, Chenglong, Wang, Xuelong, Zhang, Qinghua, Yu, Xiqian, Gu, Lin, Hu, Yong-Sheng, Li, Hong, Huang, Xuejie, Yang, Xiao-Qing, Delmas, Claude, and Chen, Liquan. Anionic Redox Reaction-Induced High-Capacity and Low-Strain Cathode with Suppressed Phase Transition. United States: N. p., 2019. Web. doi:10.1016/j.joule.2018.10.022.
Rong, Xiaohui, Hu, Enyuan, Lu, Yaxiang, Meng, Fanqi, Zhao, Chenglong, Wang, Xuelong, Zhang, Qinghua, Yu, Xiqian, Gu, Lin, Hu, Yong-Sheng, Li, Hong, Huang, Xuejie, Yang, Xiao-Qing, Delmas, Claude, & Chen, Liquan. Anionic Redox Reaction-Induced High-Capacity and Low-Strain Cathode with Suppressed Phase Transition. United States. https://doi.org/10.1016/j.joule.2018.10.022
Rong, Xiaohui, Hu, Enyuan, Lu, Yaxiang, Meng, Fanqi, Zhao, Chenglong, Wang, Xuelong, Zhang, Qinghua, Yu, Xiqian, Gu, Lin, Hu, Yong-Sheng, Li, Hong, Huang, Xuejie, Yang, Xiao-Qing, Delmas, Claude, and Chen, Liquan. 2019. "Anionic Redox Reaction-Induced High-Capacity and Low-Strain Cathode with Suppressed Phase Transition". United States. https://doi.org/10.1016/j.joule.2018.10.022.
@article{osti_1600597,
title = {Anionic Redox Reaction-Induced High-Capacity and Low-Strain Cathode with Suppressed Phase Transition},
author = {Rong, Xiaohui and Hu, Enyuan and Lu, Yaxiang and Meng, Fanqi and Zhao, Chenglong and Wang, Xuelong and Zhang, Qinghua and Yu, Xiqian and Gu, Lin and Hu, Yong-Sheng and Li, Hong and Huang, Xuejie and Yang, Xiao-Qing and Delmas, Claude and Chen, Liquan},
abstractNote = {Layered metal oxides have attracted widespread attention as cathodes for Na-ion batteries (NIBs) because of easy synthesis, highly reversible Na de-intercalation/intercalation and high energy density. However, most reported layered oxides suffer from a complex phase transition upon a large amount of Na de-intercalation. Here we report a P2-type layered oxide cathode Na0.72[Li0.24Mn0.76]O2, which exhibits exceptionally high initial charge capacity of ~210 mAh/g (0.72 Na) based on a pure Anionic Redox Reaction (ARR). Surprisingly, it is found that the global P2 structure can be maintained with minimal volume change (1.35%) upon complete removal of Na+ ions. This is due to the reduced Columbic repulsion associated with ARR and consequent suppression of the phase transition as observed in other P2-materials. Here we reveal for the first time that ARR has the functionality of stabilizing the structure, in addition to its role of increasing the capacity which has already been known. This would pave the way for the further improvement of high-energy-density NIBs.},
doi = {10.1016/j.joule.2018.10.022},
url = {https://www.osti.gov/biblio/1600597}, journal = {Joule},
issn = {2542-4351},
number = 2,
volume = 3,
place = {United States},
year = {Fri Feb 01 00:00:00 EST 2019},
month = {Fri Feb 01 00:00:00 EST 2019}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at https://doi.org/10.1016/j.joule.2018.10.022

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Cited by: 175 works
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