Simulations with machine learning potentials identify the ion conduction mechanism mediating non-Arrhenius behavior in LGPS

TL;DR

This study uses machine learning-enhanced molecular dynamics to explore ion conduction mechanisms in LGPS across a wide temperature range, revealing a phase transition near 400 K that affects ion correlation and conduction behavior.

Contribution

The paper introduces a neural network potential trained on DFT data enabling long-timescale MD simulations to analyze ion conduction in LGPS at near-DFT accuracy over a broad temperature range.

Findings

Confirmed a phase transition in LGPS around 400 K.

Observed reduced cation-cation correlation below 400 K.

Identified a shift from concerted to less correlated ion hopping near room temperature.

Abstract

Li$_{10}$Ge(PS$_6$)$_2$ (LGPS) is a highly concentrated solid electrolyte, in which Coulombic repulsion between neighboring cations is hypothesized as the underlying reason for concerted ion hopping, a mechanism common among superionic conductors such as Li$_7$La$_3$Zr$_2$O$_{12}$ (LLZO) and Li$_{1.3}$Al$_{0.3}$Ti$_{1.7}$(PO$_4$)$_3$ (LATP). While first principles simulations using molecular dynamics (MD) provide insight into the Li$^+$ transport mechanism, historically, there has been a gap in the temperature ranges studied in simulations and experiments. Here, we used a neural network (NN) potential trained on density functional theory (DFT) simulations, to run up to 40-nanosecond long MD simulations at DFT-like accuracy to characterize the ion conduction mechanisms across a range of temperatures that includes previous simulations and experimental studies. We have confirmed a Li$^+$ sublattice phase transition in LGPS around 400 K, below which the \textit{ab}-plane diffusivity $D^*_{ab}$ is drastically reduced. Concomitant with the sublattice phase transition near 400 K, there is less cation-cation (cross) correlation, as characterized by Haven ratios closer to 1, and the vibrations in the system are more harmonic at lower temperature. Intuitively, at high temperature, the collection of vibrational modes may be sufficient to drive concerted ion hops. However, near room temperature, the vibrational modes available may be insufficient to overcome electrostatic repulsion, thus resulting in less correlated ion motion and comparatively slower ion conduction. Such phenomena of a sublattice phase transition, below which concerted hopping plays a less significant role, may be extended to other highly concentrated solid electrolytes such as LLZO and LATP.