Defects in crystals alter the intrinsic nature of pristine materials including their electronic/crystalline structure and charge-transport characteristics. The ionic transport properties of solid-state ionic conductors, in particular, are profoundly affected by their defect structure. Nevertheless, a fundamental understanding of the defect structure of one of the most extensively studied lithium superionic conductors, Li₁₀GeP₂S₁₂, remains elusive because of the complexity of the structure; the effects of defects on lithium diffusion and the potential to control defects by varying synthetic conditions also remain unknown. Herein, we report, for the first time, a comprehensive first-principles study on native defects in Li₁₀GeP₂S₁₂ and their effect on lithium diffusion. We provide the complete defect profile of Li₁₀GeP₂S₁₂ and identify major defects that are easily formed regardless of the chemical environment while the presence of path-blocking defects is sensitively dependent on the synthetic conditions. Moreover, using ab initio molecular dynamics simulation, it is demonstrated that the major defects in Li₁₀GeP₂S₁₂ significantly alter the diffusion process. The defects generally facilitate lithium diffusion in Li₁₀GeP₂S₁₂ by enhancing the charge carrier concentration and flattening the site energy landscape. This work delivers a comprehensive picture of the defect chemistry and structural insights for fast lithium diffusion of Li₁₀GeP₂S₁₂-type conductors.

中文翻译：

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Li ₁₀ GeP ₂ S _12中的天然缺陷及其对锂扩散的影响

晶体中的缺陷会改变原始材料的内在性质，包括其电子/晶体结构和电荷传输特性。固态离子导体的离子传输特性尤其受到其缺陷结构的深刻影响。然而，由于结构的复杂性，对最广泛研究的锂超离子导体之一Li ₁₀ GeP ₂ S ₁₂的缺陷结构的基本了解仍然难以捉摸。缺陷对锂扩散的影响以及通过改变合成条件控制缺陷的潜力仍然未知。在此，我们首次报告了有关Li ₁₀ GeP中自然缺陷的全面的第一性原理研究₂ S ₁₂及其对锂扩散的影响。我们提供了Li ₁₀ GeP ₂ S ₁₂的完整缺陷分布图，并确定了无论化学环境如何都容易形成的主要缺陷，而路障缺陷的存在则敏感地取决于合成条件。此外，使用从头算分子动力学模拟，证明了Li ₁₀ GeP ₂ S ₁₂中的主要缺陷极大地改变了扩散过程。缺陷通常促进锂在Li ₁₀ GeP ₂ S _12中的扩散。通过提高电荷载流子浓度和平坦化站点能源格局。这项工作提供了有关Li ₁₀ GeP ₂ S ₁₂型导体快速锂扩散的缺陷化学和结构见解的全面描述。