Conduction Mechanism of Li10GeP2S12-type Lithium Superionic Conductors in a Li-Sn-Si-P-S System

被引：25

作者：

Inagaki, Makoto ^{[1
]}

Suzuki, Kota ^{[1
,2
,3
,4
]}

Hori, Satoshi ^{[3
]}

Yoshino, Kazuhiro ^{[2
]}

Matsui, Naoki ^{[2
]}

Yonemura, Masao ^{[5
]}

Hirayama, Masaaki ^{[1
,2
,3
]}

Kanno, Ryoji ^{[1
,2
,3
]}

机构：

[1] Tokyo Inst Technol, Interdisciplinary Grad Sch Sci & Engn, Dept Elect Chem, Midori Ku, 4259 Nagatsuta, Yokohama, Kanagawa 2268502, Japan

[2] Tokyo Inst Technol, Sch Mat & Chem Technol, Dept Chem Sci & Engn, Midori Ku, 4259 Nagatsuta, Yokohama, Kanagawa 2268502, Japan

[3] Tokyo Inst Technol, Inst Innovat Res, All Solid State Battery Unit, Midori Ku, 4259 Nagatsuta, Yokohama, Kanagawa 2268503, Japan

[4] Japan Sci & Technol Agcy JST, Precursory Res Embryon Sci & Technol PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama 3320012, Japan

[5] High Energy Accelerator Res Org KEK, Inst Mat Struct Sci, Neutron Sci Lab KENS, 203-1 Shirakata, Tokai, Ibaraki 3191106, Japan

来源：

CHEMISTRY OF MATERIALS | 2019年 / 31卷 / 09期

基金：

日本科学技术振兴机构; 日本学术振兴会;

关键词：

DIFFUSION;

D O I：

10.1021/acs.chemmater.9b00743

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Crystal structures of Li10GeP2S12 (LGPS)-type Li10+delta[SnySi1-y](1+delta)P2-delta S12 (Li4-x[SnySi1-y](1-x)PxS4) 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 c-axis via the Li1-Li3 sites, which indicated one-dimensional (1D) lithium diffusion for all the examined compositions. The Li10.35Sn0.27Si1.08P1.65S12 (Li3.45Sn0.09Si0.36P0.55S4) (delta = 0.35, x = 0.55, y = 0.2) system, which had the highest ionic conductivity in Li-Sn-Si-P-S system, exhibited an additional lithium diffusion pathway in the ab-plane through the Li1 and Li4 sites. High ionic conductivity (>10 mS cm(-1)) 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 c-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.

引用

页码：3485 / 3490

页数：6

共 21 条

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