Effect of Relaxations on the Conductivity of La(1/2+1/2x)Li(1/2–1/2x)Ti(1–x)Al(x)O(3) Fast Ion Conductors

[Image: see text] Perovskite-type solid-state electrolytes, Li(3x)La(2/3–x)TiO(3) (LLTO), are considered among the most promising candidates for the development of all-solid-state batteries based on lithium metal. Their high bulk ionic conductivity can be modulated by substituting part of the atoms hosted in the A- or B-site of the LLTO structure. In this work, we investigate the crystal structure and the long-range charge migration processes characterizing a family of perovskites with the general formula La(1/2+1/2x)Li(1/2–1/2x)Ti(1–x)Al(x)O(3) (0 ≤ x ≤ 0.6), in which the charge balance and the nominal A-site vacancies (n(A) = 0) are preserved. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) investigations reveal the presence of a very complex nanostructure constituted by a mixture of two different ordered nanoregions of tetragonal P4/mmm and rhombohedral R3̅c symmetries. Broadband electrical spectroscopy studies confirm the presence of different crystalline domains and demonstrate that the structural fluctuations of the BO(6) octahedra require to be intra- and intercell coupled, to enable the long-range diffusion of the lithium cation, in a similar way to the segmental mode that takes place in polymer-ion conductors. These hypotheses are corroborated by density functional theory (DFT) calculations and molecular dynamic simulations.