Abstract.
6,7Li fast magic-angle spinning solid-state nuclear magnetic resonance (NMR) spectroscopy is used to study LiMn2O4 and Li3V2(PO4)3. The presence of paramagnetic transition metal centers in these materials has a profound effect on the resulting NMR spectra. Lithium ion mobility has been studied by two-dimensional (2-D) exchange spectroscopy (EXSY) in Li3V2(PO4)3 but an absence of lithium ion exchange was observed for LiMn2O4. Several differences between the two materials are explored to explain these results. LiMn2O4 experiences a greater donation of electron spin density to the Li nucleus via the Fermi-contact interaction when compared with Li3V2(PO4)3. This contributes to a greater hyperfine chemical shift and a larger dependence of chemical shift on temperature. The delocalized electrons in LiMn2O4 cause temperature-independent T 1 relaxation rates and shorter relative T 2 values. The relative rates of ionic conductivity and spin–lattice or spin–spin relaxation in LiMn2O4 and Li3V2(PO4)3 are contrasted to illustrate the constraints on the use of 2-D EXSY to characterize ion dynamics in paramagnetic materials.
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Authors' address: Gillian R. Goward, Department of Chemistry and Brockhouse Institute for Materials Research, McMaster University, 1280 Main St. West, Hamilton, ON L8S 4M1, Canada
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Cahill, L., Chapman, R., Kirby, C. et al. The Challenge of Paramagnetism in Two-Dimensional 6,7Li Exchange NMR. Appl Magn Reson 32, 565–581 (2007). https://doi.org/10.1007/s00723-007-0046-8
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DOI: https://doi.org/10.1007/s00723-007-0046-8