MAS NMR Study of the Metastable Solid Solutions Found in the LiFePO₄/FePO₄ System

6,7 Li and 31 P NMR experiments were conducted on a series of single- or two-phase samples in the LiFePO 4 −FePO 4 system with different overall lithium contents, and containing the two end-members and/or two metastable solid solution phases, Li 0.6 FePO 4 or Li 0.34 FePO 4 . These experiments were carried out at different temperatures in order to search for vacancy/charge ordering and ion/electron mobility in the metastable phases. Evidence for Li + −Fe 2+ interactions was observed for both Li 0.6 FePO 4 and Li 0.34 FePO 4 . The strength of this interaction leads to the formation of LiFePO 4 -like clusters in the latter, as shown by the room temperature data. Different motional processes are proposed to exist as the temperature is increased and various scenarios are discussed. While concerted lithium-electron hopping and/or correlations explains the data below 125 °C, evidence for some uncorrelated motion is found at higher temperatures, together with the onset of phase mixing.