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Title: Utilizing Co 2+/Co 3+ Redox Couple in P2-Layered Na 0.66Co 0.22Mn 0.44Ti 0.34O 2 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 Na 0.66Co xMn 0.66–xTi 0.34O 2 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 Na 0.66Co xMn 0.66–xTi 0.34O 2 from orthorhombic to hexagonal is revealed when Co content increases from x = 0 to 0.33. In particular, Na 0.66Co 0.22Mn 0.44Ti 0.34O 2 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 Co 2+ substitution results in the formation of average Mn 3.7+ valence state in Na 0.66Co 0.22Mn 0.44Ti 0.34O 2, 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 Na 0.66Co 0.22Mn 0.44Ti 0.34O 2 during charge/discharge is contributed by Co 2.2+/Co 3+ and Mn 3.3+/Mn 4+ redox couples. This is themore » first time that the highly reversible Co 2+/Co 3+ 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.« less

Authors:
 [1];  [2];  [1];  [1];  [1];  [3];  [1];  [2];  [2];  [1]
  1. Fudan Univ., Shanghai (China). Department of Materials Science
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
  3. Fudan Univ., Shanghai (China). Department of Chemistry & Laser Chemistry Institute
Publication Date:
Research Org.:
Brookhaven National Lab. (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) (SC-22)
OSTI Identifier:
1368103
Alternate Identifier(s):
OSTI ID: 1368104; OSTI ID: 1376159
Report Number(s):
BNL-114116-2017-JA
Journal ID: ISSN 2198-3844; R&D Project: MA453MAEA
Grant/Contract Number:
SC0012704; AC02-06CH11357
Resource Type:
Journal Article: Published Article
Journal Name:
Advanced Science
Additional Journal Information:
Journal Volume: 4; Journal Issue: 11; Journal ID: ISSN 2198-3844
Publisher:
Wiley
Country of Publication:
United States
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 Na0.66Co0.22Mn0.44Ti 0.34O2 Cathode for Sodium-Ion Batteries. United States: N. p., 2017. Web. doi:10.1002/advs.201700219.
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 Na0.66Co0.22Mn0.44Ti 0.34O2 Cathode for Sodium-Ion Batteries. United States. doi:10.1002/advs.201700219.
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 Na0.66Co0.22Mn0.44Ti 0.34O2 Cathode for Sodium-Ion Batteries". United States. doi:10.1002/advs.201700219.
@article{osti_1368103,
title = {Utilizing Co2+/Co3+ Redox Couple in P2-Layered Na0.66Co0.22Mn0.44Ti 0.34O2 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 = 11,
volume = 4,
place = {United States},
year = {Thu Jul 06 00:00:00 EDT 2017},
month = {Thu Jul 06 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1002/advs.201700219

Citation Metrics:
Cited by: 4works
Citation information provided by
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  • Cited by 4
  • 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 Na 0.66Co xMn 0.66–xTi 0.34O 2 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 Na 0.66Co xMn 0.66–xTi 0.34O 2 from orthorhombic to hexagonal is revealed when Co content increases from x = 0 to 0.33. In particular, Na 0.66Co 0.22Mn 0.44Ti 0.34O 2 with a P2-type layered structure delivers a reversible capacity of 120more » 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 Co 2+ substitution results in the formation of average Mn 3.7+ valence state in Na 0.66Co 0.22Mn 0.44Ti 0.34O 2, 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 Na 0.66Co 0.22Mn 0.44Ti 0.34O 2 during charge/discharge is contributed by Co 2.2+/Co 3+ and Mn 3.3+/Mn 4+ redox couples. This is the first time that the highly reversible Co 2+/Co 3+ 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.« less
  • Sodium-ion batteries (SIBs) are attracting significant research attentions for large-scale energy storage applications. Cathode material is the vital part of SIBs to determine the capacity and cycle performance. Here, a series of F-doped Na 0.66[Mn 0.66Ti 0.34]O 2-xF x (x < 0.1) cathodes with tunnel structure are designed and synthesized aiming to enlarge the sodium diffusion paths. The lattice parameters of unit cell are tuned successfully by adjusting F doping amount. Na 0.66[Mn 0.66Ti 0.34]O 1.94F 0.06 with the optimized stoichiometry exhibits a reversible capacity of 97 mAh g -1 and promising cycle performance (85 mAh g -1 is maintainedmore » at 2C after 1000 cycles) with extremely low voltage polarization. More significantly, Na 0.66[Mn 0.66Ti 0.34]O 1.94F 0.06 exhibits superior low temperature performance, owing to the much enhanced thermodynamics and kinetics benefited from F doping. In conclusion, this strategy may open new opportunities to design advanced intercalation-type cathode materials for sodium ion batteries, especially for low-temperature applications.« less