Short and long range lithium motions in powder Li_1+xTi_2−xAl_x(PO₄)₃ (LTAP) NASICON compounds prepared by ceramic (x = 0.2 and 0.4) and sol–gel (x = 0.3 and 0.4) routes are discussed. ND diffraction and MAS-NMR spectroscopy were previously used to investigate structural features of these compounds. In particular, Fourier map differences showed that the amount of Li atoms allocated at M3 increases at the expense of M1 sites when the Li content increases. In this work, PFG-NMR results show that diffusion coefficients rise with the amount of lithium and temperature. The restricted diffusion inside NASICON particles is compared with “free” diffusion processes. At 300 K, diffusion coefficients D_PFG ∼ 5 × 10⁻¹² m² s⁻¹ have been deduced in ceramic x = 0.2 and 0.4 samples, decreasing with diffusion time Δ used in PFG experiments. In sol–gel samples, diffusion coefficients are near those of ceramic samples, but decrease faster with diffusion Δ times, as a consequence of the Li confinement inside sub-micrometric crystallites. The NMR spin-echo signal displays minima at specific q(γgδ) values that are related to the crystallite size. From R_dif ∼ q_m ⁻¹ distances, calculated from the position of minima, and from diffusion coefficients deduced for high Δ values, the mean crystallite size was estimated. Finally, from the temperature dependence of conductivity and diffusion coefficients, the activation energy and charge carriers concentrations were determined.

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