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The Li +  ion diffusion characteristics of V- and Nb-doped LiFePO 4  were examined with respect to undoped LiFePO 4  using muon spectroscopy (µSR) as a local probe. As little difference in diffusion coefficient between the pure and doped samples was observed, offering  D  Li  values in the range 1.8–2.3 × 10 −10  cm 2  s −1 , this implied the improvement in electrochemical performance observed within doped LiFePO 4  was not a result of increased local Li +  diffusion. This unexpected observation was made possible with the µSR technique, which can measure Li +  self-diffusion within LiFePO 4 , and therefore negated the effect of the LiFePO 4  two-phase delithiation mechanism, which has previously prevented accurate Li +  diffusion comparison between the doped and undoped materials. Therefore, the authors suggest that µSR is an excellent technique for analysing materials on a local scale to elucidate the effects of dopants on solid-state diffusion behaviour.

Mechanistic insights of Li+ diffusion within doped LiFePO4 from Muon Spectroscopy