Inagaki, Makoto Suzuki, Kota Hori, Satoshi Yoshino, Kazuhiro Matsui, Naoki Yonemura, Masao Hirayama, Masaaki Kanno, Ryoji Conduction Mechanism of Li<sub>10</sub>GeP<sub>2</sub>S<sub>12</sub>-type Lithium Superionic Conductors in a Li–Sn–Si–P–S System Crystal structures of Li<sub>10</sub>GeP<sub>2</sub>S<sub>12</sub> (LGPS)-type Li<sub>10+δ</sub>[Sn<sub><i>y</i></sub>Si<sub>1–<i>y</i></sub>]<sub>1+δ</sub>P<sub>2−δ</sub>S<sub>12</sub> (Li<sub>4–<i>x</i></sub>[Sn<sub><i>y</i></sub>Si<sub>1–<i>y</i></sub>]<sub>1–<i>x</i></sub>P<sub><i>x</i></sub>S<sub>4</sub>) solid electrolytes were analyzed by Rietveld refinement using neutron diffraction data. Maximum entropy method analysis was performed to visualize the distribution of lithium along the <i>c</i>-axis via the Li1–Li3 sites, which indicated one-dimensional (1D) lithium diffusion for all the examined compositions. The Li<sub>10.35</sub>Sn<sub>0.27</sub>Si<sub>1.08</sub>P<sub>1.65</sub>S<sub>12</sub> (Li<sub>3.45</sub>Sn<sub>0.09</sub>Si<sub>0.36</sub>P<sub>0.55</sub>S<sub>4</sub>) (δ = 0.35, <i>x</i> = 0.55, <i>y</i> = 0.2) system, which had the highest ionic conductivity in Li–Sn–Si–P–S system, exhibited an additional lithium diffusion pathway in the <i>ab</i>-plane through the Li1 and Li4 sites. High ionic conductivity (>10 mS cm<sup>–1</sup>) was achieved in the Sn–Si derivatives owing to the formation of three-dimensional (3D) ion diffusion channels. Comparison of the conductivity and related crystal structural parameters revealed the requirements for fast lithium diffusion along the <i>c</i>-axis and 3D lithium diffusion in the LGPS-type crystal structure. Large atomic displacement of the Li1 site, a large S3–S3 distance, a large bottleneck size, and small differences in Li1–Li4 distances are important for 1D and 3D lithium diffusion, respectively. Li 3.45 Sn 0.09 Si 0.36 P 0.55 S 4;3 D lithium diffusion;Maximum entropy method analysis;lithium diffusion;ion diffusion channels;lithium diffusion pathway;Li 4 sites;Li 10.35 Sn 0.27 Si 1.08 P 1.65 S 12;neutron diffraction data;Li 1 site;Li 10 GeP 2 S 12;type Lithium Superionic Conductors;LGPS-type crystal structure 2019-04-16
    https://acs.figshare.com/articles/journal_contribution/Conduction_Mechanism_of_Li_sub_10_sub_GeP_sub_2_sub_S_sub_12_sub_-type_Lithium_Superionic_Conductors_in_a_Li_Sn_Si_P_S_System/8026841
10.1021/acs.chemmater.9b00743.s001