New structures and compositions as inorganic solid-state electrolytes (ISSEs) are needed for all-solid-state lithium batteries (ASSLBs). Here we report the theoretical discovery of three new structure types by computational identification of nearest neighbor Li–Li distance (nR_Li-Li) within Li-ion sublattice of fluorides which correlates with ISSEs ionic conductivity. This is achieved by computing Li-ions radial distribution functions and whose first peak corresponds to nR_Li-Li. Subsequent theoretical exploration of the four fluorides with small nR_Li-Li affords three materials (Li₃MF₆ (M = Al, Sc, Ga)) with crystal structures featuring three-dimensional diffusion channels for Li-ions. The three fluoride materials exhibit very well (electro)chemical stability and high ionic conductivity. The screening method used in this work will accelerate the systematic discovery of high ionic conductivity ISSEs for use in ASSLBs and related applications.

全固态锂电池（ASSLB）需要新的结构和成分作为无机固态电解质（ISSE）。在这里，我们通过计算识别与ISSE离子电导率相关的氟化物锂离子亚晶格内最近邻Li-Li距离（n R _Li-Li），报告了三种新结构类型的理论发现。这可以通过计算锂离子的径向分布函数来实现，并且其第一峰对应于n R _Li-Li。随后用小n R _Li-Li对四种氟化物进行理论探索，得到了三种材料（Li ₃ MF ₆（M = Al，Sc，Ga）），其晶体结构具有针对Li离子的三维扩散通道。三种氟化物材料具有非常好的（电化学）化学稳定性和高离子电导率。这项工作中使用的筛选方法将加快对用于ASSLB和相关应用的高离子电导率ISSE的系统发现。