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Title: Tuning P2-Structured Cathode Material by Na-Site Mg Substitution for Na-Ion Batteries

Abstract

Most of P2-type layered oxides suffer from multiple voltage plateaus, due to Na+/vacancy-order superstructures caused by strong interplay between Na-Na electrostatic interactions and charge ordering in the transition-metal layers. In this paper, Mg-ions are successfully introduced into Na sites in addition to the conventional transition metal sites in P2-type Na0.7[Mn0.6Ni0.4]O2 as new cathode materials for sodium-ion batteries. Mg-ions in Na layer serve as “pillar” to stabilize the layered structure, especially for high voltage charging meanwhile Mg-ions in transition metal layer can destroy charge ordering. More importantly, Mg ion occupation in both sodium and transition metal layers will be able to create “Na-O-Mg” and “Mg-O-Mg” configurations in layered structure, resulting in ionic O 2p character, which allocates these O 2p states on top of those interact with transition metals in O-valence band, thus promoting reversible oxygen redox. This innovative design contributes smooth voltage profile and high structural stability. Na0.7Mg0.05[Mn0.6Ni0.2Mg0.15]O2 exhibits superior electrochemical performance, especially good capacity retention at high current rate under a high cut-off voltage (4.2 V). A new P2 phase is formed after charge, rather than O2 phase for the unsubstituted material. Besides, multiple intermediate phases are observed during high-rate charging. Na-ion transport kinetics are mainly affected by elemental-relatedmore » redox couple and structural reorganization. In conclusion, these findings will open new opportunities for designing and optimizing layer-structured cathodes for sodium-ion batteries.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3];  [2];  [1]
+ Show Author Affiliations
  1. Fudan Univ., Shanghai (China)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1488528
Report Number(s):
BNL-209807-2018-JAAM
Journal ID: ISSN 0002-7863
Grant/Contract Number:  
SC0012704; AC02-05CH11231; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 2; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; Na-ion Battery; Mg Substitution; Cathode materials; P2-structure; X-ray absorption spectroscopy

Citation Formats

Wang, Qin-Chao, Meng, Jing-Ke, Yue, Xin-Yang, Qiu, Qi-Qi, Song, Yun, Wu, Xiao-Jing, Fu, Zheng-Wen, Xia, Yong-Yao, Shadike, Zulipiya, Wu, Jinpeng, Yang, Xiao-Qing, and Zhou, Yong-Ning. Tuning P2-Structured Cathode Material by Na-Site Mg Substitution for Na-Ion Batteries. United States: N. p., 2018. Web. doi:10.1021/jacs.8b08638.
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Wang, Qin-Chao, Meng, Jing-Ke, Yue, Xin-Yang, Qiu, Qi-Qi, Song, Yun, Wu, Xiao-Jing, Fu, Zheng-Wen, Xia, Yong-Yao, Shadike, Zulipiya, Wu, Jinpeng, Yang, Xiao-Qing, & Zhou, Yong-Ning. Tuning P2-Structured Cathode Material by Na-Site Mg Substitution for Na-Ion Batteries. United States. https://doi.org/10.1021/jacs.8b08638
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Wang, Qin-Chao, Meng, Jing-Ke, Yue, Xin-Yang, Qiu, Qi-Qi, Song, Yun, Wu, Xiao-Jing, Fu, Zheng-Wen, Xia, Yong-Yao, Shadike, Zulipiya, Wu, Jinpeng, Yang, Xiao-Qing, and Zhou, Yong-Ning. Tue . "Tuning P2-Structured Cathode Material by Na-Site Mg Substitution for Na-Ion Batteries". United States. https://doi.org/10.1021/jacs.8b08638. https://www.osti.gov/servlets/purl/1488528.
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@article{osti_1488528,
title = {Tuning P2-Structured Cathode Material by Na-Site Mg Substitution for Na-Ion Batteries},
author = {Wang, Qin-Chao and Meng, Jing-Ke and Yue, Xin-Yang and Qiu, Qi-Qi and Song, Yun and Wu, Xiao-Jing and Fu, Zheng-Wen and Xia, Yong-Yao and Shadike, Zulipiya and Wu, Jinpeng and Yang, Xiao-Qing and Zhou, Yong-Ning},
abstractNote = {Most of P2-type layered oxides suffer from multiple voltage plateaus, due to Na+/vacancy-order superstructures caused by strong interplay between Na-Na electrostatic interactions and charge ordering in the transition-metal layers. In this paper, Mg-ions are successfully introduced into Na sites in addition to the conventional transition metal sites in P2-type Na0.7[Mn0.6Ni0.4]O2 as new cathode materials for sodium-ion batteries. Mg-ions in Na layer serve as “pillar” to stabilize the layered structure, especially for high voltage charging meanwhile Mg-ions in transition metal layer can destroy charge ordering. More importantly, Mg ion occupation in both sodium and transition metal layers will be able to create “Na-O-Mg” and “Mg-O-Mg” configurations in layered structure, resulting in ionic O 2p character, which allocates these O 2p states on top of those interact with transition metals in O-valence band, thus promoting reversible oxygen redox. This innovative design contributes smooth voltage profile and high structural stability. Na0.7Mg0.05[Mn0.6Ni0.2Mg0.15]O2 exhibits superior electrochemical performance, especially good capacity retention at high current rate under a high cut-off voltage (4.2 V). A new P2 phase is formed after charge, rather than O2 phase for the unsubstituted material. Besides, multiple intermediate phases are observed during high-rate charging. Na-ion transport kinetics are mainly affected by elemental-related redox couple and structural reorganization. In conclusion, these findings will open new opportunities for designing and optimizing layer-structured cathodes for sodium-ion batteries.},
doi = {10.1021/jacs.8b08638},
journal = {Journal of the American Chemical Society},
number = 2,
volume = 141,
place = {United States},
year = {Tue Dec 18 00:00:00 EST 2018},
month = {Tue Dec 18 00:00:00 EST 2018}
}
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https://doi.org/10.1021/jacs.8b08638
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    Works referencing / citing this record:

    Deciphering an Abnormal Layered‐Tunnel Heterostructure Induced by Chemical Substitution for the Sodium Oxide Cathode
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    O3‐Type Layered Ni‐Rich Oxide: A High‐Capacity and Superior‐Rate Cathode for Sodium‐Ion Batteries
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