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Title: Anionic redox reaction in layered NaCr2/3Ti1/3S2 through electron holes formation and dimerization of S–S

Abstract

The use of anion redox reactions is gaining interest for increasing rechargeable capacities in alkaline ion batteries. Although anion redox coupling of S2- and (S2)2- through dimerization of S–S in sulfides have been studied and reported, an anion redox process through electron hole formation has not been investigated to the best of our knowledge. Here, we report an O3-NaCr2/3Ti1/3S2 cathode that delivers a high reversible capacity of ~186 mAh g-1 (0.95 Na) based on the cation and anion redox process. Various charge compensation mechanisms of the sulfur anionic redox process in layered NaCr2/3Ti1/3S2, which occur through the formation of disulfide-like species, the precipitation of elemental sulfur, S–S dimerization, and especially through the formation of electron holes, are investigated. Direct structural evidence for formation of electron holes and (S2)n- species with shortened S–S distances is obtained. These results provide valuable information for the development of materials based on the anionic redox reaction.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3];  [4];  [1]; ORCiD logo [5];  [6]; ORCiD logo [3];  [3];  [7];  [6];  [8];  [1]
  1. Fudan Univ., Shanghai (China)
  2. Chinese Academy of Sciences (CAS), Shanghai (China); Chinese Academy of Sciences (CAS), Beijing (China)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Nanjing Univ.of Science and Technology, Nanjing, Jiangsu (China)
  5. Chinese Academy of Sciences (CAS), Beijing (China)
  6. Shanghai Jiao Tong Univ. (China)
  7. Stony Brook Univ., NY (United States)
  8. Chinese Academy of Sciences (CAS), Shanghai (China); Tianmu Lake Institute of Advanced Energy Storage Technologies, Liyang City, Jiangsu (China); ShanghaiTech Univ. (China)
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)
OSTI Identifier:
1569554
Report Number(s):
BNL-212161-2019-JAAM
Journal ID: ISSN 2041-1723
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wang, Tian, Ren, Guo-Xi, Shadike, Zulipiya, Yue, Ji-Li, Cao, Ming-Hui, Zhang, Jie-Nan, Chen, Ming-Wei, Yang, Xiao-Qing, Bak, Seong-Min, Northrup, Paul, Liu, Pan, Liu, Xiao-Song, and Fu, Zheng-Wen. Anionic redox reaction in layered NaCr2/3Ti1/3S2 through electron holes formation and dimerization of S–S. United States: N. p., 2019. Web. doi:10.1038/s41467-019-12310-6.
Wang, Tian, Ren, Guo-Xi, Shadike, Zulipiya, Yue, Ji-Li, Cao, Ming-Hui, Zhang, Jie-Nan, Chen, Ming-Wei, Yang, Xiao-Qing, Bak, Seong-Min, Northrup, Paul, Liu, Pan, Liu, Xiao-Song, & Fu, Zheng-Wen. Anionic redox reaction in layered NaCr2/3Ti1/3S2 through electron holes formation and dimerization of S–S. United States. doi:10.1038/s41467-019-12310-6.
Wang, Tian, Ren, Guo-Xi, Shadike, Zulipiya, Yue, Ji-Li, Cao, Ming-Hui, Zhang, Jie-Nan, Chen, Ming-Wei, Yang, Xiao-Qing, Bak, Seong-Min, Northrup, Paul, Liu, Pan, Liu, Xiao-Song, and Fu, Zheng-Wen. Tue . "Anionic redox reaction in layered NaCr2/3Ti1/3S2 through electron holes formation and dimerization of S–S". United States. doi:10.1038/s41467-019-12310-6. https://www.osti.gov/servlets/purl/1569554.
@article{osti_1569554,
title = {Anionic redox reaction in layered NaCr2/3Ti1/3S2 through electron holes formation and dimerization of S–S},
author = {Wang, Tian and Ren, Guo-Xi and Shadike, Zulipiya and Yue, Ji-Li and Cao, Ming-Hui and Zhang, Jie-Nan and Chen, Ming-Wei and Yang, Xiao-Qing and Bak, Seong-Min and Northrup, Paul and Liu, Pan and Liu, Xiao-Song and Fu, Zheng-Wen},
abstractNote = {The use of anion redox reactions is gaining interest for increasing rechargeable capacities in alkaline ion batteries. Although anion redox coupling of S2- and (S2)2- through dimerization of S–S in sulfides have been studied and reported, an anion redox process through electron hole formation has not been investigated to the best of our knowledge. Here, we report an O3-NaCr2/3Ti1/3S2 cathode that delivers a high reversible capacity of ~186 mAh g-1 (0.95 Na) based on the cation and anion redox process. Various charge compensation mechanisms of the sulfur anionic redox process in layered NaCr2/3Ti1/3S2, which occur through the formation of disulfide-like species, the precipitation of elemental sulfur, S–S dimerization, and especially through the formation of electron holes, are investigated. Direct structural evidence for formation of electron holes and (S2)n- species with shortened S–S distances is obtained. These results provide valuable information for the development of materials based on the anionic redox reaction.},
doi = {10.1038/s41467-019-12310-6},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
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Figures / Tables:

Figure 1 Figure 1: Electrochemical performance of NaCr1-yTiyS2 series. a, Voltage profile for the NaCr1-yTiyS2 series versus Na+/Na at C/10 rate. The Coulombic efficiency of NaCr2/3Ti1/3S2 at the first cycle is superior to 100% for there are few Na vacancies in the pristine material without Na precursor excess. b, The voltage profilemore » over first 50 cycles for a Na/NaCr2/3Ti1/3S2 cell together with (as inset) its capacity retention in range of 1.4-2.55 V, 2.55-2.85 V and 2.95-3.3 V at C/10 rate. c, First four cyclic voltammograms for the NaCr2/3Ti1/3S2 electrode cycled between 3.3 V and 1.4 V.« less

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