  Garnet-type Li7La3Zr2O12 (LLZO) is a solid electrolyte material with a
low-conductivity tetragonal and a high-conductivity cubic phase. Using
density-functional theory and variable cell shape molecular dynamics
simulations, we show that the tetragonal phase stability is dependent on a
simultaneous ordering of the Li ions on the Li sublattice and a
volume-preserving tetragonal distortion that relieves internal structural
strain. Supervalent doping introduces vacancies into the Li sublattice,
increasing the overall entropy and reducing the free energy gain from ordering,
eventually stabilizing the cubic phase. We show that the critical temperature
for cubic phase stability is lowered as Li vacancy concentration (dopant level)
is raised and that an activated hop of Li ions from one crystallographic site
to another always accompanies the transition. By identifying the relevant
mechanism and critical concentrations for achieving the high conductivity
phase, this work shows how targeted synthesis could be used to improve
electrolytic performance.
