Anion charge-lattice volume dependent Li ion migration in compounds with the face-centered cubic anion frameworks

TL;DR

This study investigates how anion charge and lattice volume influence lithium ion migration in face-centered cubic frameworks, proposing new design principles for superionic conductors based on these factors.

Contribution

It introduces a novel approach to designing superionic conductors by linking anion charge and lattice volume to lithium ion migration barriers within fcc frameworks.

Findings

Large negative anion charges increase lithium stability in tetrahedral sites.

Larger lattice volumes favor tetrahedral lithium occupation.

Adjusting electronegativity differences can lower lithium migration barriers.

Abstract

The 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 frameworks were creatively constructed to study the effects of anion charge and lattice volume on the stability of lithium ion occupation and lithium ion migration. Both the large negative anion charges and large lattice volumes would increase the relative stabilities of lithium-anion tetrahedron, and make Li ions prefer to occupy the tetrahedral sites. For a tetrahedral Li 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 Li ion migration to its adjacent octahedral site through a tetrahedral transition state, the larger negative anion charge is, the lower the lithium ion migration barrier will be. New design principles for developing superionic conductors with the fcc anion framework were proposed. Low Li ion migration barriers would be achieved by adjusting the non-lithium elements within the same crystal structure framework to obtain the desired electronegativity difference between the anion element and non-lithium cation element.