Crystal Structures and Phase Stability of the LiS-PS System from First Principles.

The LiS-PS pseudo-binary system has been a valuable source of promising superionic conductors, with α-LiPS, β-LiPS, HT-LiPS, and LiPS having excellent room-temperature Li-ion conductivity >0.1 mS/cm. The metastability of these phases at ambient temperature motivates a study to quantify their thermodynamic accessibility. Through calculating the electronic, configurational, and vibrational sources of free energy from first principles, a phase diagram of the crystalline LiS-PS space is constructed. New ground-state orderings are proposed for α-LiPS, HT-LiPS, LT-LiPS, and LiPS. Well-established phase stability trends from experiments are recovered, such as polymorphic phase transitions in LiPS and LiPS, and the instability of LiPS at high temperature. At ambient temperature, it is predicted that all superionic conductors in this space are indeed metastable but thermodynamically accessible. Vibrational and configurational sources of entropy are shown to be essential toward describing the stability of superionic conductors. New details of the Li sublattices are revealed and are found to be crucial toward accurately predicting configurational entropy. All superionic conductors contain significant configurational entropy, which suggests an inherent correlation between fast Li diffusion and thermodynamic stability arising from the configurational disorder.