LiInCl (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.

中文翻译：

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研究 Li3InCl6 晶体结构的堆叠变化及其对固体电解质性能的影响


LiInCl（LIC）最近成为一种有前景的卤化物固体电解质，用于全固态锂电池。本研究研究了 LIC 的结构特征，特别关注潜在的堆垛层错及其对固体电解质性能的影响。通过第一性原理计算进行的晶体堆叠结构的热力学评估表明，相对于先前报道的参考LIC结构，[010]方向堆叠序列的某些变化导致晶体能量降低，这意味着热力学上更有利的新晶体LIC 的结构比现有的参考结构。这种新型晶体结构（称为#7-8）的功效是根据有关锂离子迁移率和电化学稳定性的参考结构进行评估的。结果表明，离子电导率显着增强，同时保持了相当的电化学稳定性窗口。研究表明，LIC 晶体内特定堆叠结构的修改可以通过在特定方向上为锂离子建立低能垒路径来增强锂离子电导率。虽然其他方向的迁移率可能会降低，但这会导致锂离子电导率的整体改善。与传统的参考结构相比，所提出的晶体结构表现出优异的热力学稳定性，并且与实验获得的X射线衍射数据一致，强调了其作为未来LIC晶体结构分析的新基准的潜力。此外，这项研究表明，二维缺陷（例如堆垛层错）可能在影响卤化物固体电解质的性能方面发挥着至关重要的作用。