@ARTICLE{10.3389/fenrg.2016.00022, AUTHOR={Baba, Takeshi and Kawamura, Yoshiumi}, TITLE={Structure and Ionic Conductivity of Li2S–P2S5 Glass Electrolytes Simulated with First-Principles Molecular Dynamics}, JOURNAL={Frontiers in Energy Research}, VOLUME={4}, YEAR={2016}, URL={https://www.frontiersin.org/articles/10.3389/fenrg.2016.00022}, DOI={10.3389/fenrg.2016.00022}, ISSN={2296-598X}, ABSTRACT={Lithium thiophosphate-based materials are attractive as solid electrolytes in all-solid-state lithium batteries because glass or glass-ceramic structures of these materials are associated with very high conductivity. In this work, we modeled lithium thiophosphates with amorphous structures and investigated Li+ mobilities by using molecular dynamics calculations based on density functional theory (DFT-MD). The structures of xLi2S–(100 − x)P2S5 (x = 67, 70, 75, and 80) were created by randomly identifying appropriate compositions of Li+, PS43,P2S74, and S2− and then annealing them with DFT-MD calculations. Calculated relative stabilities of the amorphous structures with x = 67, 70, and 75 to crystals with the same compositions were 0.04, 0.12, and 0.16 kJ/g, respectively. The implication is that these amorphous structures are metastable. There was good agreement between calculated and experimental structure factors determined from X-ray scattering. The differences between the structure factors of amorphous structures were small, except for the first sharp diffraction peak, which was affected by the environment between Li and S atoms. Li+ diffusion coefficients obtained from DFT-MD calculations at various temperatures for picosecond simulation times were on the order of 10−3–10−5 Å2/ps. Ionic conductivities evaluated by the Nernst–Einstein relationship at 298.15 K were on the order of 10−5 S/cm. The ionic conductivity of the amorphous structure with x = 75 was the highest among the amorphous structures because there was a balance between the number density and diffusibility of Li+. The simulations also suggested that isolated S atoms suppress Li+ migration.} }