Probing Oxygen Motion in Disordered Anionic Conductors with 17O and 51V MAS NMR Spectroscopy

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Science  23 Aug 2002:
Vol. 297, Issue 5585, pp. 1317-1320
DOI: 10.1126/science.1074130

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Identification of the local environments of the ions in a solid-state electrolyte that contribute to the ionic conductivity or remain trapped in the lattice represents a challenge for many experimental probes of structure. We show that high-resolution17O magic angle spinning nuclear magnetic resonance (MAS NMR) spectra may be obtained even from the highly disordered, layered materials α-Bi4V2O11 and γ-Bi4V1.7Ti0.3O10.85, in which the different oxide sites in the lattice may be distinguished. The sites responsible for anionic conduction were determined directly from the variable-temperature 17O NMR spectra, and correlation times for motion were estimated. Double-resonance17O/51V NMR methods were used as confirmation of the assignments of the resonances and as a second experimental probe of motion that is sensitive to mobility involving oxide ion hops between the same crystallographic sites.

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