Lithium mobility in LiM2(PO4)3 compounds, with M= Ge, Ti, Sn, Zr and Hf, has been investigated by
Li Nuclear Magnetic Resonance (NMR) spectroscopy in the temperature range 100-500 K. From the analysis of
Li NMR quadrupole interactions (CQ and η parameters), Li sites occupancy and exchange processes between structural sites have been studied. Below 250K, Li ions are preferentially located at M1 sites in rhombohedral phases, but occupy M12 sites in triclinic ones. At increasing temperatures, Li mobility has been deduced from spin-spin () and spin-lattice relaxation () rates. In this analysis, the presence of two relaxation mechanisms in plots has been associated with departures of conductivity from the Arrhenius behavior. At high temperatures, residence times at M12−T11−T11−T
1 and M12 sites become similar and conductivity significantly increase. This superionic state can be achieved by enlarged order-disorder transformations in rhombohedral phases, or by sharp first order transitions in triclinic ones. Results described in the LiTi2(PO4)3 sample have been compared with those obtained in rhombohedral Li1+xTi2-xAlx(PO4)3 and LiTi2-xZrx(PO4)3 series showing respectively higher and lower conductivities. In the case of Li1.2Ti1.8Al0.2(PO4)3, displaying the highest reported conductivity, NMR results are discussed in relation with those obtained by Neutron Diffraction (ND) and Impedance Spectroscopy (IS). Diffusion coefficients determined by NMR Pulse Field Gradient (PFG) technique are similar to those deduced from Impedance Spectroscopy and NMR relaxation data.