title: Structural and electronic features of binary Li₂S-P₂S₅ glasses.
abstract: The atomic and electronic structures of binary Li2S-P2S5 glasses used as solid electrolytes are modeled by a combination of density functional theory (DFT) and reverse Monte Carlo (RMC) simulation using synchrotron X-ray diffraction, neutron diffraction, and Raman spectroscopy data. The ratio of PSx polyhedral anions based on the Raman spectroscopic results is reflected in the glassy structures of the 67Li2S-33P2S5, 70Li2S-30P2S5, and 75Li2S-25P2S5 glasses, and the plausible structures represent the lithium ion distributions around them. It is found that the edge sharing between PSx and LiSy polyhedra increases at a high Li2S content, and the free volume around PSx polyhedra decreases. It is conjectured that Li(+) ions around the face of PSx polyhedra are clearly affected by the polarization of anions. The electronic structure of the DFT/RMC model suggests that the electron transfer between the P ion and the bridging sulfur (BS) ion weakens the positive charge of the P ion in the P2S7 anions. The P2S7 anions of the weak electrostatic repulsion would causes it to more strongly attract Li(+) ions than the PS4 and P2S6 anions, and suppress the lithium ionic conduction. Thus, the control of the edge sharing between PSx and LiSy polyhedra without the electron transfer between the P ion and the BS ion is expected to facilitate lithium ionic conduction in the above solid electrolytes.
authors.affiliation: Office of Society-Academia Collaboration for Innovation, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan.
authors.forename: Koji
authors.initials: K
authors.lastname: Ohara
authors.affiliation: Office of Society-Academia Collaboration for Innovation, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan.|Material Analysis Department, Material Development Division, TOYOTA MOTOR CORPORATION, 1, Toyota-cho, Toyota, Aichi 471-8572, Japan.
authors.forename: Akio
authors.initials: A
authors.lastname: Mitsui
authors.affiliation: Office of Society-Academia Collaboration for Innovation, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan.
authors.forename: Masahiro
authors.initials: M
authors.lastname: Mori
authors.affiliation: Research Reactor Institute, Kyoto University, 2-1010 Asashiro-Nishi, Kumatori-cho, Sennan-gun, Osaka 590-0494, Japan.
authors.forename: Yohei
authors.initials: Y
authors.lastname: Onodera
authors.affiliation: Office of Society-Academia Collaboration for Innovation, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan.
authors.forename: Shinya
authors.initials: S
authors.lastname: Shiotani
authors.affiliation: Office of Society-Academia Collaboration for Innovation, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan.
authors.forename: Yukinori
authors.initials: Y
authors.lastname: Koyama
authors.affiliation: Graduate School of Human and Environmental Studies, Kyoto University, Yoshida-nihonmatsu-cho, Sakyo-ku, Kyoto 606-8501, Japan.
authors.forename: Yuki
authors.initials: Y
authors.lastname: Orikasa
authors.affiliation: Office of Society-Academia Collaboration for Innovation, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan.
authors.forename: Miwa
authors.initials: M
authors.lastname: Murakami
authors.affiliation: Office of Society-Academia Collaboration for Innovation, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan.
authors.forename: Keiji
authors.initials: K
authors.lastname: Shimoda
authors.affiliation: Research Reactor Institute, Kyoto University, 2-1010 Asashiro-Nishi, Kumatori-cho, Sennan-gun, Osaka 590-0494, Japan.
authors.forename: Kazuhiro
authors.initials: K
authors.lastname: Mori
authors.affiliation: Research Reactor Institute, Kyoto University, 2-1010 Asashiro-Nishi, Kumatori-cho, Sennan-gun, Osaka 590-0494, Japan.
authors.forename: Toshiharu
authors.initials: T
authors.lastname: Fukunaga
authors.affiliation: Office of Society-Academia Collaboration for Innovation, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan.
authors.forename: Hajime
authors.initials: H
authors.lastname: Arai
authors.affiliation: Graduate School of Human and Environmental Studies, Kyoto University, Yoshida-nihonmatsu-cho, Sakyo-ku, Kyoto 606-8501, Japan.
authors.forename: Yoshiharu
authors.initials: Y
authors.lastname: Uchimoto
authors.affiliation: Office of Society-Academia Collaboration for Innovation, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan.
authors.forename: Zempachi
authors.initials: Z
authors.lastname: Ogumi