biostudies-literatureKam RLVehicle Technologies Office9111-9126https://www.ebi.ac.uk/biostudies/studies/S-EPMC10653090biostudies-literatureUnknown35(21)The Li₂S-P₂S₅ pseudo-binary system has been a valuable source of promising superionic conductors, with α-Li₃PS₄, β-Li₃PS₄, HT-Li₇PS₆, and Li₇P₃S₁₁ 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 Li₂S-P₂S₅ space is constructed. New ground-state orderings are proposed for α-Li₃PS₄, HT-Li₇PS₆, LT-Li<subChemistry of materials : a publication of the American Chemical SocietyCrystal Structures and Phase Stability of the Li₂S-P₂S₅ System from First Principles.PMC10653090DE-AC02-05CH11231Yang JHXie FBarroso-Luque LKam RLJun KCeder GfalseCrystal Structures and Phase Stability of the Li₂S-P₂S₅ System from First Principles.The Li₂S-P₂S₅ pseudo-binary system has been a valuable source of promising superionic conductors, with α-Li₃PS₄, β-Li₃PS₄, HT-Li₇PS₆, and Li₇P₃S₁₁ 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 Li₂S-P₂S₅ space is constructed. New ground-state orderings are proposed for α-Li₃PS₄, HT-Li₇PS₆, LT-Li<sub2023-01-01T00:00:00Z2023 Nov2026-06-03T11:51:10.559Z2026-05-29T03:06:17.283ZS-EPMC106530903802754310.1021/acs.chemmater.3c01793