Proper design principles are essential for the efficient development of superionic conductors. However, the existing design principles are mainly proposed from the perspective of crystal structures. In this work, the face-centered cubic (fcc) anion sublattices were creatively constructed to study the effects of anion charge and lattice volume on the stability of lithium ion occupation and lithium ion migration by the density functional theory calculations. Both the large negative anion charges and large lattice volumes would increase the relative stabilities of lithium-anion tetrahedron, making lithium ions prefer to occupy the tetrahedral sites. For a tetrahedral lithium ion migration to its adjacent tetrahedral site through an octahedral transition state, the smaller the negative anion charge is, the lower the lithium ion migration barrier will be. While for an octahedral lithium ion migration to its adjacent octahedral site through a tetrahedral transition state, the more negative anion charge is, the lower the lithium ion migration barrier will be. New design principles for developing and optimizing superionic conductors with the fcc anion sublattice were proposed. Low lithium ion migration barriers would be achieved by adjusting the non-lithium elements within the same crystal structure to obtain the desired electronegativity difference between the anion element and the non-lithium cation element.

正确的设计原则对于有效开发超离子导体至关重要。然而，现有的设计原理主要是从晶体结构的角度提出的。在这项工作中，面心立方（fcc）创造性地构建了阴离子亚晶格，以通过密度泛函理论计算来研究阴离子电荷和晶格体积对锂离子占据稳定性和锂离子迁移的影响。较大的负阴离子电荷和较大的晶格体积都将增加锂阴离子四面体的相对稳定性，使锂离子更喜欢占据四面体位点。对于四面体锂离子通过八面体过渡态迁移至其相邻的四面体位点，负电荷越小，锂离子迁移势垒就越低。对于八面体锂离子通过四面体过渡态迁移到其相邻的八面体位点而言，负电荷越多，锂离子的迁移势垒就越低。提出了fcc阴离子亚晶格。通过调节同一晶体结构内的非锂元素以获得阴离子元素与非锂阳离子元素之间所需的电负性差异，可以实现低锂离子迁移势垒。