Abstract.
31P nuclear magnetic resonance (NMR) shifts on the order of thousands of parts per million are observed for olivine LiMPO4 (M = Mn, Fe, Co, Ni) samples, a promising class of Li ion rechargeable battery electrode materials. Variable-temperature 31P NMR measurements of shift are used to determine that the supertransferred hyperfine interaction is the dominant mechanism giving rise to these unusually large observed 31P shifts. Various models for predicting 31P and 7Li shifts in LiMPO4 (M = Mn, Fe, Co, Ni) were investigated. Alloys of LiFe1−x Mn x PO4, where x varies from 0 to 1, were also investigated by 7Li NMR. Covalency constants, calculated from variable-temperature NMR shifts and magnetic susceptibility data, are determined for the P–O–M bonds in LiMPO4 (M = Mn, Fe, Co, Ni) and compared to the covalency constants of the Li–O–M bond. The sign and relative magnitude of the covalency constants are discussed in terms of positive and negative spin densities at the nuclei of interest. The covalency constants for the Li–O–M and P–O–M bonds were measured for Li1.8Na0.2FeMn2(PO4)3 and compared to the covalency constants measured in the olivine LiMPO4 (M = Mn, Fe, Co, Ni) samples. The Li1.8Na0.2FeMn2(PO4)3 structure has a volume per transition metal atom and Li–O–M bond distances that are similar to those of the olivine LiMPO4 (M = Mn, Fe, Co, Ni) samples.
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Authors' address: Jeffrey A. Reimer, Department of Chemical Engineering, University of California Berkeley, Berkeley, CA 94720, USA
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Wilcke, S., Lee, YJ., Cairns, E. et al. Covalency Measurements via NMR in Lithium Metal Phosphates. Appl Magn Reson 32, 547–563 (2007). https://doi.org/10.1007/s00723-007-0032-1
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DOI: https://doi.org/10.1007/s00723-007-0032-1