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NaV1.25Ti0.75O4: A Potential Post-Spinel Cathode Material for Mg Batteries

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Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada
Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, United States
Cite this: Chem. Mater. 2018, 30, 1, 121–128
Publication Date (Web):November 8, 2017
Copyright © 2017 American Chemical Society

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    Rechargeable Mg batteries are promising candidates for high energy density storage in theory, when a Mg metal anode is combined with an oxide cathode material. Despite the widely observed sluggish Mg2+ diffusion in most oxide lattices, recent first-principles calculations predicted low diffusion barriers in the calcium ferrite (CF)-type post-spinel structures. In the present work, we experimentally examine the prospect of CF-type NaV1.25Ti0.75O4 as a Mg cathode. The Na+ ions, which lie in the ion migration pathway, need to be removed or exchanged with Mg2+ to allow Mg2+ de/intercalation. Partial desodiation was achieved through chemical and electrochemical methods, as proven by X-ray diffraction and X-ray absorption spectroscopy, but deep desodiation was accompanied by partial amorphization of the material. Mg2+ ion exchange at moderate temperature (80 °C) resulted in the formation of Na0.19Mg0.41V1.25Ti0.75O4; however, phase transformation was observed when higher temperatures were applied to attempt complete ion exchange. Such phenomena point to the instability of the CF lattice when the tunnel is empty or occupied by a small ion (Mg2+). Thus, while the low migration barrier predicted by computation is partly based on the relative metastability of the theoretical CF-MgxV1.25Ti0.75O4 lattice, the difficulty in stabilizing it also renders the material synthetically nonaccessible, hindering this post-spinel’s application as an electrode material.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.7b03383.

    • Refined parameters and crystalline phase weight percentages for the pristine, desodiated, Mg ion exchanged NaV1.25Ti0.75O4 samples; XAS of the pristine, desodiated, and Mg ion exchanged samples measured for various materials in the full energy range at the V L3-, Ti L2,3-, and O K-edges with total electron and fluorescence yields complete V L2,3 spectra; Ti 2p XPS spectrum; charge/discharge profiles for Na-ion de/insertion in NaV1.25Ti0.75O4 in a Na cell (PDF)

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