Li mobility in the orthorhombic Li0.18La0.61TiO3 perovskite studied by NMR and impedance spectroscopies

Electrical conductivity and NMR relaxation times (T-1 and T-2) have been determined in the Li0.18La0.61TiO3 perovskite. At room temperature, the unit cell constants are a = 3.865(1), b = 3.876(1), and c = 7.788(2) Angstrom and the space group Pmmm (orthorhombic). In this doubled perovskite, the Rietveld analysis of the X-ray powder pattern showed that La ions occupy preferentially one type of sites (z/c = 0), and Li and vacancies accommodate with the remaining La at the second site (z/c = 0.5). From this fact, Li motion should be favored in the plane ab; however, exchanges of Li between contiguous layers are detected above 200 K by NMR spectroscopy. From T-1 and T-2 NMR data, two main relaxation mechanisms have been detected, which have been ascribed to localized exchanges (200-273 K) and extended motions of Li (above 273 K). The de conductivity shows a non-Arrhenius temperature dependence, and local activation energies of 0.41 and 0.26 eV were obtained in the low- and high-temperature ranges, respectively. Both NMR and electrical conductivity relaxations are described by stretched exponential functions, characteristic of correlated ion motions.