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Title: Utilizing Co2+/Co3+ Redox Couple in P2-Layered Na0.66Co0.22 Mn0.44Ti0.34O2 Cathode for Sodium-Ion Batteries

Abstract

Developing sodium-ion batteries for large-scale energy storage applications is facing big challenges of the lack of high-performance cathode materials. Here, a series of new cathode materials Na0.66CoxMn0.66–xTi0.34O2 for sodium-ion batteries are designed and synthesized aiming to reduce transition metal-ion ordering, charge ordering, as well as Na+ and vacancy ordering. An interesting structure change of Na0.66CoxMn0.66–xTi0.34O2 from orthorhombic to hexagonal is revealed when Co content increases from x = 0 to 0.33. In particular, Na0.66Co0.22Mn0.44Ti0.34O2 with a P2-type layered structure delivers a reversible capacity of 120 mAh g-1 at 0.1 C. When the current density increases to 10 C, a reversible capacity of 63.2 mAh g-1 can still be obtained, indicating a promising rate capability. The low valence Co2+ substitution results in the formation of average Mn3.7+ valence state in Na0.66Co0.22Mn0.44Ti0.34O2, effectively suppressing the Mn3+-induced Jahn–Teller distortion, and in turn stabilizing the layered structure. X-ray absorption spectroscopy results suggest that the charge compensation of Na0.66Co0.22Mn0.44Ti0.34O2 during charge/discharge is contributed by Co2.2+/Co3+ and Mn3.3+/Mn4+ redox couples. This is the first time that the highly reversible Co2+/Co3+ redox couple is observed in P2-layered cathodes for sodium-ion batteries. This finding may open new approaches to design advanced intercalation-type cathode materials.

Authors:
 [1];  [2];  [1];  [1];  [1];  [3];  [1];  [2];  [2];  [1]
+ Show Author Affiliations
  1. Department of Materials Science, Fudan University, Shanghai 200433 P. R. China
  2. Chemistry Division, Brookhaven National Laboratory, Upton NY 11973 USA
  3. Department of Chemistry & Laser Chemistry Institute, Fudan University, Shanghai 200433 P. R. China
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1368103
Alternate Identifier(s):
OSTI ID: 1368104; OSTI ID: 1376159
Report Number(s):
BNL-114116-2017-JA
Journal ID: ISSN 2198-3844; 1700219
Grant/Contract Number:  
AC02-06CH11357; SC0012704
Resource Type:
Published Article
Journal Name:
Advanced Science
Additional Journal Information:
Journal Name: Advanced Science; Journal ID: ISSN 2198-3844
Publisher:
Wiley
Country of Publication:
Germany
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; National Synchrotron Light Source

Citation Formats

Wang, Qin-Chao, Hu, Enyuan, Pan, Yang, Xiao, Na, Hong, Fan, Fu, Zheng-Wen, Wu, Xiao-Jing, Bak, Seong-Min, Yang, Xiao-Qing, and Zhou, Yong-Ning. Utilizing Co2+/Co3+ Redox Couple in P2-Layered Na0.66Co0.22 Mn0.44Ti0.34O2 Cathode for Sodium-Ion Batteries. Germany: N. p., 2017. Web. doi:10.1002/advs.201700219.
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Wang, Qin-Chao, Hu, Enyuan, Pan, Yang, Xiao, Na, Hong, Fan, Fu, Zheng-Wen, Wu, Xiao-Jing, Bak, Seong-Min, Yang, Xiao-Qing, & Zhou, Yong-Ning. Utilizing Co2+/Co3+ Redox Couple in P2-Layered Na0.66Co0.22 Mn0.44Ti0.34O2 Cathode for Sodium-Ion Batteries. Germany. https://doi.org/10.1002/advs.201700219
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Wang, Qin-Chao, Hu, Enyuan, Pan, Yang, Xiao, Na, Hong, Fan, Fu, Zheng-Wen, Wu, Xiao-Jing, Bak, Seong-Min, Yang, Xiao-Qing, and Zhou, Yong-Ning. Thu . "Utilizing Co2+/Co3+ Redox Couple in P2-Layered Na0.66Co0.22 Mn0.44Ti0.34O2 Cathode for Sodium-Ion Batteries". Germany. https://doi.org/10.1002/advs.201700219.
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@article{osti_1368103,
title = {Utilizing Co2+/Co3+ Redox Couple in P2-Layered Na0.66Co0.22 Mn0.44Ti0.34O2 Cathode for Sodium-Ion Batteries},
author = {Wang, Qin-Chao and Hu, Enyuan and Pan, Yang and Xiao, Na and Hong, Fan and Fu, Zheng-Wen and Wu, Xiao-Jing and Bak, Seong-Min and Yang, Xiao-Qing and Zhou, Yong-Ning},
abstractNote = {Developing sodium-ion batteries for large-scale energy storage applications is facing big challenges of the lack of high-performance cathode materials. Here, a series of new cathode materials Na0.66CoxMn0.66–xTi0.34O2 for sodium-ion batteries are designed and synthesized aiming to reduce transition metal-ion ordering, charge ordering, as well as Na+ and vacancy ordering. An interesting structure change of Na0.66CoxMn0.66–xTi0.34O2 from orthorhombic to hexagonal is revealed when Co content increases from x = 0 to 0.33. In particular, Na0.66Co0.22Mn0.44Ti0.34O2 with a P2-type layered structure delivers a reversible capacity of 120 mAh g-1 at 0.1 C. When the current density increases to 10 C, a reversible capacity of 63.2 mAh g-1 can still be obtained, indicating a promising rate capability. The low valence Co2+ substitution results in the formation of average Mn3.7+ valence state in Na0.66Co0.22Mn0.44Ti0.34O2, effectively suppressing the Mn3+-induced Jahn–Teller distortion, and in turn stabilizing the layered structure. X-ray absorption spectroscopy results suggest that the charge compensation of Na0.66Co0.22Mn0.44Ti0.34O2 during charge/discharge is contributed by Co2.2+/Co3+ and Mn3.3+/Mn4+ redox couples. This is the first time that the highly reversible Co2+/Co3+ redox couple is observed in P2-layered cathodes for sodium-ion batteries. This finding may open new approaches to design advanced intercalation-type cathode materials.},
doi = {10.1002/advs.201700219},
journal = {Advanced Science},
number = ,
volume = ,
place = {Germany},
year = {Thu Jul 06 00:00:00 EDT 2017},
month = {Thu Jul 06 00:00:00 EDT 2017}
}
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https://doi.org/10.1002/advs.201700219
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