{"title":"Investigating stacking variations in Li3InCl6 crystal structure and their influence on solid electrolyte properties","authors":"Yongseon Kim , Sungho Choi","doi":"10.1016/j.actamat.2024.120135","DOIUrl":null,"url":null,"abstract":"<div><p>Li<sub>3</sub>InCl<sub>6</sub> (LIC) has recently emerged as a promising halide-based solid electrolyte for all-solid-state Li batteries. This study investigates the structural characteristics of LIC, with a specific focus on potential stacking faults and their impact on the properties of the solid electrolyte. A thermodynamic assessment of crystallographic stacking structures, conducted via first-principles calculations, reveals that certain variations in stacking sequences in the [010] direction relative to the previously reported reference LIC structure result in reduced crystal energy, which implies a thermodynamically more favorable new crystal structure for LIC than the extant reference structure. The efficacy of this novel crystal structure, referred to as #7–8, is evaluated against the reference structure concerning Li-ion mobility and electrochemical stability. The results demonstrate a notable enhancement in ionic conductivity while preserving a comparable electrochemical stability window. Modifications in specific stacking configurations within LIC crystals are shown to enhance Li-ion conductivity by establishing low-energy barrier pathways for Li ions in particular directions. While the mobility in other directions may decrease, this result in an overall improvement in Li-ion conductivity. The proposed crystal structure demonstrates superior thermodynamic stability compared to the conventional reference structure and is consistent with experimentally obtained X-ray diffraction data, underscoring its potential as a novel benchmark for future analyses of LIC crystal structures. Furthermore, this study suggests that two-dimensional defects, such as stacking faults, may play a crucial role in influencing the performance of halide-based solid electrolytes.</p></div>","PeriodicalId":238,"journal":{"name":"Acta Materialia","volume":null,"pages":null},"PeriodicalIF":8.3000,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Acta Materialia","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1359645424004865","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Li3InCl6 (LIC) has recently emerged as a promising halide-based solid electrolyte for all-solid-state Li batteries. This study investigates the structural characteristics of LIC, with a specific focus on potential stacking faults and their impact on the properties of the solid electrolyte. A thermodynamic assessment of crystallographic stacking structures, conducted via first-principles calculations, reveals that certain variations in stacking sequences in the [010] direction relative to the previously reported reference LIC structure result in reduced crystal energy, which implies a thermodynamically more favorable new crystal structure for LIC than the extant reference structure. The efficacy of this novel crystal structure, referred to as #7–8, is evaluated against the reference structure concerning Li-ion mobility and electrochemical stability. The results demonstrate a notable enhancement in ionic conductivity while preserving a comparable electrochemical stability window. Modifications in specific stacking configurations within LIC crystals are shown to enhance Li-ion conductivity by establishing low-energy barrier pathways for Li ions in particular directions. While the mobility in other directions may decrease, this result in an overall improvement in Li-ion conductivity. The proposed crystal structure demonstrates superior thermodynamic stability compared to the conventional reference structure and is consistent with experimentally obtained X-ray diffraction data, underscoring its potential as a novel benchmark for future analyses of LIC crystal structures. Furthermore, this study suggests that two-dimensional defects, such as stacking faults, may play a crucial role in influencing the performance of halide-based solid electrolytes.
期刊介绍:
Acta Materialia serves as a platform for publishing full-length, original papers and commissioned overviews that contribute to a profound understanding of the correlation between the processing, structure, and properties of inorganic materials. The journal seeks papers with high impact potential or those that significantly propel the field forward. The scope includes the atomic and molecular arrangements, chemical and electronic structures, and microstructure of materials, focusing on their mechanical or functional behavior across all length scales, including nanostructures.