Role of Pairwise Reactions on the Synthesis of LiLaTiO and the Resulting Structure-Property Correlations.

The performance of single-ion conductors is highly sensitive to the material's defect chemistry. Tuning these defects is limited for solid-state reactions as they occur at particle-particle interfaces, which provide a complex evolving energy landscape for atomic rearrangement and product formation. In this report, we investigate the (1) order of addition and (2) lithium precursor decomposition temperature and their effect on the synthesis and grain boundary conductivity of the perovskite lithium lanthanum titanium oxide (LLTO). We use an intimately mixed sol-gel, a solid-state reaction of Li precursor + LaO + TiO, and Li precursor + amorphous LaTiO as different chemical routes to change the way in which the elements are brought together. The results show that the perovskite can accommodate a wide range of Li deficiencies (upward of 50%) while maintaining the tetragonal LLTO structure, indicating that X-ray diffraction (XRD) is insufficient to fully characterize the chemical nature of the product (i.e., Li-deficient LLTO may behave differently than stoichiometric LLTO). Variations in the relative intensities of different reflections in XRD suggest variations in the La ordering within the crystal structure between synthesis methods. Furthermore, the choice of the precursor and the order of addition of the reactants lower the time required to form a pure phase. Density functional theory calculations of the formation energy of possible reaction intermediates support the hypothesis that a greater thermodynamic driving force to form LLTO leads to a greater LLTO yield. The retention of lithium is correlated with the thermal decomposition temperature of the Li precursor and the starting material mixing strategy. Taking the results together suggests that cations that share a site with Li should be mixed early to avoid ordering. Such cation ordering inhibits Li motion, leading to higher Li ion resistance.