Comparison of the polymorphs of VOPO4 as multi-electron cathodes for rechargeable alkali-ion batteries

Lin, Yuh-Chieh; Hidalgo, Marc F.  V.; Chu, Iek-Heng; Chernova, Natasha A.; Whittingham, M. Stanley; Ong, Shyue Ping

doi:10.1039/c7ta04558a

Comparison of the polymorphs of VOPO₄ as multi-electron cathodes for rechargeable alkali-ion batteries

Journal Article · Sun Jan 01 00:00:00 EST 2017 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/c7ta04558a· OSTI ID:1493610

^[1]; Hidalgo, Marc F. V. ^[2]; Chu, Iek-Heng ^[1]; Chernova, Natasha A. ^[2]; ^[2]; ^[1]

Univ. of California, San Diego, CA (United States). Department of NanoEngineering
Binghamton Univ., NY (United States). NECCES

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 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 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.

Research Organization:: Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

DOE Contract Number:: SC0012583

OSTI ID:: 1493610

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 33 Vol. 5; ISSN JMCAET; ISSN 2050-7488

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

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