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Title: Conversion reaction of vanadium sulfide electrode in the lithium-ion cell: Reversible or not reversible?

Abstract

With the increasing interest in transition metal chalcogenides, sulfide minerals containing the disulfide unit (S22-) have gained intensive attention for potential applications in energy storage devices, such as lithium-ion batteries (LIBs). Vanadium tetrasulfide (VS4) possesses a unique linear-chain structure with a Peierls distortion and shows great promise for application in LIBs. However, its electrochemical reaction mechanism is still controversial, mainly due to the amorphous nature of the intermediates and final products. Here, by applying multiple X-ray spectroscopies, we reveal that VS4 undergoes lithium intercalation and conversion reactions sequentially during the first discharge process, which are partially reversible in the subsequent charge process. However, an anomalous intercalation/conversion mixed reaction mechanism is dominant for the second cycle, mainly owing to the amorphization of the VS4 electrode during the first cycle. In addition, the sulfur atoms are also involved in the redox reaction during cycling, with the anionic contribution of S22- ↔ 2S2- transformation. Furthermore, we find that the formation process of the solid electrolyte interphase is highly dynamic during the discharge and charge processes. Finally, the present study provides deeper insights into the complex reaction mechanism of VS4. This knowledge can accelerate the development of high-performance VS4-based electrode materials for LIBs.

Authors:
 [1];  [2];  [3];  [3];  [4];  [1];  [4]; ORCiD logo [5];  [6];  [7]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  2. Univ. of California, Los Angeles, CA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. Univ. of Science and Technology of China, Hefei (China)
  5. Wuhan Univ. (China)
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS); Univ. of California, Santa Cruz, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1530373
Alternate Identifier(s):
OSTI ID: 1548032
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Nano Energy
Additional Journal Information:
Journal Volume: 51; Journal Issue: C; Journal ID: ISSN 2211-2855
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Zhang, Liang, Wei, Qiulong, Sun, Dan, Li, Ning, Ju, Huanxin, Feng, Jun, Zhu, Junfa, Mai, Liqiang, Cairns, Elton J., and Guo, Jinghua. Conversion reaction of vanadium sulfide electrode in the lithium-ion cell: Reversible or not reversible?. United States: N. p., 2018. Web. doi:10.1016/j.nanoen.2018.06.076.
Zhang, Liang, Wei, Qiulong, Sun, Dan, Li, Ning, Ju, Huanxin, Feng, Jun, Zhu, Junfa, Mai, Liqiang, Cairns, Elton J., & Guo, Jinghua. Conversion reaction of vanadium sulfide electrode in the lithium-ion cell: Reversible or not reversible?. United States. doi:10.1016/j.nanoen.2018.06.076.
Zhang, Liang, Wei, Qiulong, Sun, Dan, Li, Ning, Ju, Huanxin, Feng, Jun, Zhu, Junfa, Mai, Liqiang, Cairns, Elton J., and Guo, Jinghua. Sat . "Conversion reaction of vanadium sulfide electrode in the lithium-ion cell: Reversible or not reversible?". United States. doi:10.1016/j.nanoen.2018.06.076. https://www.osti.gov/servlets/purl/1530373.
@article{osti_1530373,
title = {Conversion reaction of vanadium sulfide electrode in the lithium-ion cell: Reversible or not reversible?},
author = {Zhang, Liang and Wei, Qiulong and Sun, Dan and Li, Ning and Ju, Huanxin and Feng, Jun and Zhu, Junfa and Mai, Liqiang and Cairns, Elton J. and Guo, Jinghua},
abstractNote = {With the increasing interest in transition metal chalcogenides, sulfide minerals containing the disulfide unit (S22-) have gained intensive attention for potential applications in energy storage devices, such as lithium-ion batteries (LIBs). Vanadium tetrasulfide (VS4) possesses a unique linear-chain structure with a Peierls distortion and shows great promise for application in LIBs. However, its electrochemical reaction mechanism is still controversial, mainly due to the amorphous nature of the intermediates and final products. Here, by applying multiple X-ray spectroscopies, we reveal that VS4 undergoes lithium intercalation and conversion reactions sequentially during the first discharge process, which are partially reversible in the subsequent charge process. However, an anomalous intercalation/conversion mixed reaction mechanism is dominant for the second cycle, mainly owing to the amorphization of the VS4 electrode during the first cycle. In addition, the sulfur atoms are also involved in the redox reaction during cycling, with the anionic contribution of S22- ↔ 2S2- transformation. Furthermore, we find that the formation process of the solid electrolyte interphase is highly dynamic during the discharge and charge processes. Finally, the present study provides deeper insights into the complex reaction mechanism of VS4. This knowledge can accelerate the development of high-performance VS4-based electrode materials for LIBs.},
doi = {10.1016/j.nanoen.2018.06.076},
journal = {Nano Energy},
number = C,
volume = 51,
place = {United States},
year = {2018},
month = {9}
}

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Works referencing / citing this record:

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  • DOI: 10.3390/en12061074