Microscopic dynamics of lithium diffusion in single crystal of the solid-state electrolyte La$_{2/3-x}$Li$_{3x}$TiO$_{3}$ ($x=0.13$) studied by quasielastic neutron scattering

TL;DR

This study combines quasielastic neutron scattering and molecular dynamics to elucidate the microscopic lithium ion diffusion mechanisms in La$_{2/3-x}$Li$_{3x}$TiO$_{3}$, revealing quasi-isotropic three-dimensional diffusion and insights for enhancing oxide electrolyte conductivity.

Contribution

It provides the first detailed microscopic analysis of Li$^+$ diffusion in LLTO using QENS and MD, clarifying conduction pathways and activation energies.

Findings

Li$^+$ diffusion is quasi-isotropic in LLTO.

Self-diffusion coefficients are comparable to sulfide conductors.

Diffusion follows a thermally activated process.

Abstract

Quasielastic neutron scattering (QENS) measurements combined with first principles based moleculardynamics calculations were conducted to study the dynamics of Li$^+$ ions in a solid-state electrolyte La$_{2/3-x}$Li$_{3x}$TiO$_{3}$ (LLTO) with $x=0.13$. By using a large $^7$Li-enriched single crystal sample, a QENS signal was clearly observed along the three principal axes [110], [111], and [001] at a temperature ($T$) of 600 K. Wave vector dependence of the linewidth of the QENS signal along each direction was explained well using the Chudley-Elliot model for jumps between the A sites of the perovskite lattice through the bottleneck square, which was also supported by molecular dynamics calculations. At $T=600$ K, the estimated self-diffusion coefficient of Li$^+$ ($D_{Li}$) in the $ab$ plane [$D^{ab}_{Li}=(6.8\pm0.5)\times 10^{-6}$ cm$^2$/s] was slightly larger than that along the $c$ axis [$D^{c}_{Li}=(4.4\pm0.3)\times 10^{-6}$ cm$^2$/s], suggesting quasi-isotropic diffusion, that is, the three-dimensional diffusion of Li$^+$ ions. The decrease in $D_{Li}$ with decreasing $T$ was reasonably explained by a thermal activation process with the activation energy determined from ionic-conductivity measurements. Furthermore, the estimated values of the self-diffusion coefficient of Li$^+$ ions are comparable to those in the sulfide-based Li$^+$ ion conductor, Li$_{7}$P$_{3}$S$_{11}$, although its ionic conductivity is 10 times larger than that for LLTO. The obtained microscopic information on Li$^+$ diffusion in LLTO clarifies how to understand the Li conduction mechanism in LLTO and Li$_{7}$P$_{3}$S$_{11}$ in a unified manner and can provide a way to increase the Li$^+$ ionic conductivity in oxide-based solid electrolytes.