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Title: Comparison of the polymorphs of VOPO 4 as multi-electron cathodes for rechargeable alkali-ion batteries

Abstract

Multi-electron polyanion cathodes offer the potential for achieving both high voltage and high capacity in rechargeable alkali-ion batteries. Among the few materials known to exhibit multi-electron cycling, the polymorphs of VOPO 4, which operate on the V 3+–V 4+–V 5+ redox couples, are particularly promising due to the high gravimetric capacities that have been achieved and the high voltage of the V 4+/5+ couple. In this work, we performed a systematic first principles investigation, supported by careful electrochemical characterization and published experimental data, of the relative thermodynamic stability, voltage, band gap, and diffusion kinetics for alkali intercalation into the β, ε and αI polymorphs of VOPO 4. We find that all VOPO4 polymorphs remain reasonably stable with the insertion of one alkali ion per V, but are significantly destabilized with the insertion of two alkali ions per V. The voltages for Na insertion are ~0.33–0.69 V lower than those for Li insertion. We find that the αI polymorph is predicted to have higher Li + migration barriers and larger band gaps than the β and ε polymorphs, which account for the relatively worse electrochemical cycling performance observed. On the other hand, only the αI polymorph exhibits reasonably low barriers formore » Na + migration compared to the β and ε polymorphs, which are consistent with observed electrochemical performances reported thus far in the literature. We also show that differences in the voltage, kinetics and rate capability of these different polymorphs for Li and Na insertion can be traced back to their fundamentally different VO 6/VO 5-PO 4 frameworks.« less

Authors:
ORCiD logo [1];  [2];  [1];  [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of California, San Diego, CA (United States). Department of NanoEngineering
  2. Binghamton Univ., NY (United States). NECCES
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1493610
DOE Contract Number:  
SC0012583
Resource Type:
Journal Article
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 5; Journal Issue: 33; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

Lin, Yuh-Chieh, Hidalgo, Marc F. V., Chu, Iek-Heng, Chernova, Natasha A., Whittingham, M. Stanley, and Ong, Shyue Ping. Comparison of the polymorphs of VOPO4 as multi-electron cathodes for rechargeable alkali-ion batteries. United States: N. p., 2017. Web. doi:10.1039/c7ta04558a.
Lin, Yuh-Chieh, Hidalgo, Marc F. V., Chu, Iek-Heng, Chernova, Natasha A., Whittingham, M. Stanley, & Ong, Shyue Ping. Comparison of the polymorphs of VOPO4 as multi-electron cathodes for rechargeable alkali-ion batteries. United States. doi:10.1039/c7ta04558a.
Lin, Yuh-Chieh, Hidalgo, Marc F. V., Chu, Iek-Heng, Chernova, Natasha A., Whittingham, M. Stanley, and Ong, Shyue Ping. Sun . "Comparison of the polymorphs of VOPO4 as multi-electron cathodes for rechargeable alkali-ion batteries". United States. doi:10.1039/c7ta04558a.
@article{osti_1493610,
title = {Comparison of the polymorphs of VOPO4 as multi-electron cathodes for rechargeable alkali-ion batteries},
author = {Lin, Yuh-Chieh and Hidalgo, Marc F. V. and Chu, Iek-Heng and Chernova, Natasha A. and Whittingham, M. Stanley and Ong, Shyue Ping},
abstractNote = {Multi-electron polyanion cathodes offer the potential for achieving both high voltage and high capacity in rechargeable alkali-ion batteries. Among the few materials known to exhibit multi-electron cycling, the polymorphs of VOPO4, which operate on the V3+–V4+–V5+ redox couples, are particularly promising due to the high gravimetric capacities that have been achieved and the high voltage of the V4+/5+ couple. In this work, we performed a systematic first principles investigation, supported by careful electrochemical characterization and published experimental data, of the relative thermodynamic stability, voltage, band gap, and diffusion kinetics for alkali intercalation into the β, ε and αI polymorphs of VOPO4. We find that all VOPO4 polymorphs remain reasonably stable with the insertion of one alkali ion per V, but are significantly destabilized with the insertion of two alkali ions per V. The voltages for Na insertion are ~0.33–0.69 V lower than those for Li insertion. We find that the αI polymorph is predicted to have higher Li+ migration barriers and larger band gaps than the β and ε polymorphs, which account for the relatively worse electrochemical cycling performance observed. On the other hand, only the αI polymorph exhibits reasonably low barriers for Na+ migration compared to the β and ε polymorphs, which are consistent with observed electrochemical performances reported thus far in the literature. We also show that differences in the voltage, kinetics and rate capability of these different polymorphs for Li and Na insertion can be traced back to their fundamentally different VO6/VO5-PO4 frameworks.},
doi = {10.1039/c7ta04558a},
journal = {Journal of Materials Chemistry. A},
issn = {2050-7488},
number = 33,
volume = 5,
place = {United States},
year = {2017},
month = {1}
}

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