Proton Diffusion in Orthorhombic Perovskite Sulfides

IF 7 2区材料科学 Q2 CHEMISTRY, PHYSICAL Chemistry of Materials Pub Date : 2025-02-14 DOI:10.1021/acs.chemmater.4c01841

Stefan Walder, Aurelie Gueguen, Denis Kramer

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Abstract

The proton mobility in perovskite sulfides is investigated. Both stable as well as unstable compounds are considered to cover a wide range of ABS₃ compounds, the latter were selected based on a preferably small energy difference to the thermodynamic phase equilibrium. Density functional theory (DFT) is used to analyze all possible metastable hydrogen positions within the (001) and (110)/(11̅0) planes spanned by the sulfur atoms. The nudged elastic band (NEB) method is used to determine the activation energy barriers between neighboring hydrogen sites. From the hydrogen positions and the activation energies, the diffusion rate is calculated with an approach based on the Markovian master equation. Proton mobility is analyzed in detail for a subset of compounds, while a simplified analysis of the zigzag-paths in the prominent [001] and [010] directions is used to explore a wider chemical space. Room temperature diffusion coefficients of the order of 10^–6 cm²/s are predicted to be feasible in Zr-based compounds. The A- and B-site occupants influence mobility mainly due to their impact on crystallography, because symmetry-breaking distortions that reduce the S–S distance have a leading influence on reducing activation energies, but they also induce significant anisotropy.

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正交钙钛矿硫化物中的质子扩散

研究了钙钛矿硫化物中质子的迁移率。稳定化合物和不稳定化合物都被认为涵盖了广泛的ABS3化合物，后者是基于热力学相平衡的较小能量差而选择的。用密度泛函理论（DFT）分析了硫原子所跨越的（001）和(110)/(11)平面内所有可能的亚稳氢位置。采用微推弹性带（NEB）方法确定相邻氢位之间的活化能垒。根据氢的位置和活化能，采用基于马尔可夫主方程的方法计算扩散速率。质子迁移的详细分析了一个子集的化合物，而在突出的[001]和[010]方向上的曲折路径的简化分析被用来探索更广泛的化学空间。预测zr基化合物的室温扩散系数为10-6 cm2/s。A位和b位占据者对迁移率的影响主要是由于其对晶体学的影响，因为减少S-S距离的对称破缺扭曲对降低活化能有主要影响，但它们也会引起显著的各向异性。

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来源期刊

Chemistry of Materials 工程技术-材料科学：综合

CiteScore

14.10

自引率

5.80%

发文量

929

审稿时长

1.5 months

期刊介绍： The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.