Atomistic mechanisms underlying the maximum in diffusivity in doped Li$_7$La$_3$Zr$_2$O$_{12}$

TL;DR

This study uses molecular dynamics simulations to reveal that the maximum ionic diffusivity in doped Li7La3Zr2O12 arises from a balance between vacancy concentration and Li+ site occupancy, influenced by temperature and doping levels.

Contribution

It provides a detailed atomistic understanding of how doping and site occupancy affect diffusivity maxima in LLZO solid electrolytes.

Findings

Maximum diffusivity results from competing effects of vacancy concentration and site occupancy.

Li+ concentration has a dominant influence on transport at high temperatures.

Doping increases vacancies but also raises activation energy due to site occupancy.

Abstract

Doped lithium lanthanum zirconium oxide (LLZO) is a promising class of solid electrolytes for lithium-ion batteries due to their good electrochemical stability and compatibility with Li metal anodes. Ionic diffusivity in these ceramics is known to occur via correlated, vacancy mediated, jumps of Li+ between alternating tetrahedral and octahedral sites. Aliovalent doping at the Zr-site increases the concentration of vacancies in the Li+ sublattice and cation diffusivity, but such an increase is universally followed by a decrease for Li+ concentration lower than 6.3 - 6.5 Li molar content. Molecular dynamics simulations based on density functional theory show that the maximum in diffusivity originates from competing effects between the increased vacancy concentration and the increasing occupancy of the low-energy tetrahedral sites by Li+, which increases the overall activation energy associated with diffusion. For the relatively high temperatures of our simulations, Li+ concentration plays a dominant role in transport as compared to dopant chemistry.