We investigated the structural and electronic descriptors for atmospheric instability of Li-thiophosphates (β-Li₃PS₄) using density functional theory. Based on thermodynamic and crystallographic considerations, four stable surfaces such as (111), (101), (001), and (100) were identified in β-Li₃PS₄ using the equilibrium crystal shape according to Gibbs-Wulff theorem. As such, the p-band center of the S-ion (∆E_p) and segregation energy of S vacancy (E_{VS^∙∙, seg}) were utilized as electronic and structural descriptors to evaluate the atmospheric instability of β-Li₃PS₄. It was determined that the (110) and (111) surfaces led to high surface instability among the four surfaces. Furthermore, it was observed that the p-band center and the segregation energy of S have a linear relationship (i.e., ∆E_p increased as E_{VS^∙∙, seg} decreased), which could be used as simple descriptors to evaluate the atmospheric instability of sulfide-based Li-ion conductors.

我们使用密度泛函理论研究了硫代磷酸锂（β -Li ₃ PS ₄）的大气不稳定性的结构和电子描述符。基于热力学和晶体学的考虑，根据吉布斯-沃尔夫定理，使用平衡晶体形状在β- Li ₃ PS ₄中确定了四个稳定表面，例如（111），（101），（001）和（100）。因此，S离子的p带中心（∆E _p）和S空位的偏析能（E _{V S ^∙∙，seg}）用作电子和结构描述符来评估β- Li ₃ PS ₄的大气不稳定性。可以确定（110）和（111）表面导致四个表面之间的高表面不稳定性。此外，观察到的是，p波段中心和S的偏析能量具有线性关系（即，ΔE _p随着ë _{V小号^∙∙，SEG}降低），其可以被用作简单的描述符，以评估大气硫化物基锂离子导体的不稳定性。