Fluoride-ion conductivity of scheelite-type LiYb1-xMxF4±x (M = Mg, Ca, Sr, Hf)

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics Pub Date : 2025-04-02 DOI:10.1016/j.ssi.2025.116851

Kota Onuki , Naoki Matsui , Kota Suzuki , Masaaki Hirayama , Ryoji Kanno

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引用次数: 0

Abstract

Fluorite-type fluoride-ion conductors have been widely studied, whereas fluorite-derivative structures remain untapped material spaces as fluoride-ion conductors. In this study, fluoride-ion conductivities in scheelite-type LiYb_1-xM_xF_4±x (M = Mg, Ca, Sr, and Hf) solid solutions were investigated. Introduction of fluorine-vacancy through aliovalent cation-substitution significantly enhanced ionic conductivity, with 15 % Ca²⁺ substitution for Yb³⁺ exhibiting a maximum conductivity of 1.7 × 10⁻⁵ S cm⁻¹ at 473 K. Structural analysis confirmed the formation of F vacancies, whereas bond valence energy landscape calculations revealed low-barrier conduction pathways. Furthermore, molecular dynamics simulations revealed distinct fluoride migration pathway near the Ca²⁺-doped and undoped regions. These findings offer new insights into the fluoride-ion conduction mechanisms in fluorite-related structures.

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萤石型氟离子导体已被广泛研究，而萤石衍生物结构作为氟离子导体的材料空间仍有待开发。本研究调查了白钨矿型 LiYb1-xMxF4±x（M = Mg、Ca、Sr 和 Hf）固溶体的氟离子电导率。结构分析证实了 F 空位的形成，而键价能谱计算则揭示了低势垒传导途径。此外，分子动力学模拟揭示了掺 Ca2+ 和未掺 Ca2+ 区域附近不同的氟化物迁移途径。这些发现为了解萤石相关结构中氟离子的传导机制提供了新的视角。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Solid State Ionics 物理-物理：凝聚态物理

CiteScore

6.10

自引率

3.10%

发文量

152

审稿时长

58 days

期刊介绍： This interdisciplinary journal is devoted to the physics, chemistry and materials science of diffusion, mass transport, and reactivity of solids. The major part of each issue is devoted to articles on: (i) physics and chemistry of defects in solids; (ii) reactions in and on solids, e.g. intercalation, corrosion, oxidation, sintering; (iii) ion transport measurements, mechanisms and theory; (iv) solid state electrochemistry; (v) ionically-electronically mixed conducting solids. Related technological applications are also included, provided their characteristics are interpreted in terms of the basic solid state properties. Review papers and relevant symposium proceedings are welcome.