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Mitigating Cation Diffusion Limitations and Intercalation-Induced Framework Transitions in a 1D Tunnel-Structured Polymorph of V2O5

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    Mitigating Cation Diffusion Limitations and Intercalation-Induced Framework Transitions in a 1D Tunnel-Structured Polymorph of V2O5
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    † Department of Chemistry, Texas A&M University, Ross@Spence Street, College Station, Texas 77845-3012, United States
    ‡ Department of Materials Science and Engineering, Texas A&M University, 575 Ross Street, College Station, Texas 77843-3003, United States
    § The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
    ∥ Department of Physics, Applied Physics and Astronomy, Binghamton University, Binghamton, New York 13902, United States
    ⊥ Materials Science & Engineering, Binghamton University, Binghamton New York 13902, United States
    # Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, United States
    *E-mail: [email protected]
    *E-mail: [email protected]
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    Chemistry of Materials

    Cite this: Chem. Mater. 2017, 29, 24, 10386–10397
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    https://doi.org/10.1021/acs.chemmater.7b03800
    Published December 12, 2017
    Copyright © 2017 American Chemical Society
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    Abstract

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    The design of cathodes for intercalation batteries requires consideration of both atomistic and electronic structure to facilitate redox at specific transition metal sites along with the concomitant diffusion of cations and electrons. Cation intercalation often brings about energy dissipative phase transformations that give rise to substantial intercalation gradients as well as multiscale phase and strain inhomogeneities. The layered α-V2O5 phase is considered to be a classical intercalation host but is plagued by sluggish diffusion kinetics and a series of intercalation-induced phase transitions that require considerable lattice distortion. Here, we demonstrate that a 1D tunnel-structured ζ-phase polymorph of V2O5 provides a stark study in contrast and can reversibly accommodate Li-ions without a large distortion of the structural framework and with substantial mitigation of polaronic confinement. Entirely homogeneous lithiation is evidenced across multiple cathode particles (in contrast to α-V2O5 particles wherein lithiation-induced phase transformations induce phase segregation). Barriers to Li-ion as well as polaron diffusion are substantially diminished for metastable ζ-V2O5 in comparison to the thermodynamically stable α-V2O5 phase. The rigid tunnel framework, relatively small changes in coordination environment of intercalated Li-ions across the diffusion pathways defined by the 1D tunnels, and degeneracy of V 3d states at the bottom of the conduction band reduce electron localization that is a major impediment to charge transport in α-V2O5. The 1D ζ-phase thus facilitates a continuous lithiation pathway that is markedly different from the successive intercalation-induced phase transitions observed in α-V2O5. The results here illustrate the importance of electronic structure in mediating charge transport in oxide cathode materials and demonstrates that a metastable polymorph with higher energy bonding motifs that define frustrated coordination environments can serve as an attractive intercalation host.

    Copyright © 2017 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.7b03800.

    • Select bond distance and bond angles for ζ- and β-LixV2O5 phases; charge density changes and DOS for single electron reduced ζ-V2O5–, and the effect of spin degeneracy upon polaron formation (PDF)

    • Video S1: transformation pathway as deduced from the Amplimodes program (MPG)

    • Video S2: the coupled motion of the polaron as well as the Li-ions through the tunnels of the 1D ζ-V2O5 phase (MPG)

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    This article is cited by 27 publications.

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    Cite this: Chem. Mater. 2017, 29, 24, 10386–10397
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.chemmater.7b03800
    Published December 12, 2017
    Copyright © 2017 American Chemical Society
    Request reuse permissions

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