Can Strain or Anion Interchange Make an Unstable Structure Stable? Energetics, Lattice Dynamics and Strain-Tunable Band Gaps of Lithium Chalcohalide Antiperovskites (Li${}_3$$BA$) and their Anion Interchange Variants (Li${}_3$$AB$)

Abstract

Lithium chalcohalide antiperovskites are a promising, non-toxic alternative to lead halide perovskites, with potential as solid electrolytes for Li-ion batteries. we computationally investigate a relatively unexplored anion-interchange mechanism by which cubic Li${}_3$$AB$ derivatives are obtained from the parent cubic antiperovskite Li${}_3$$BA$ ($A$ = O, S, Se, Te, Po; $B$ = F, Cl, Br, I). The calculated relative energy landscape provides a useful guide for anion-site selectivity and its role in structural stability. The energetic stability results reveal that the smaller anion inside the octahedron stabilizes the structures. The lattice-dynamic calculations confirm that Li${}_3$F$A$ ($A$ = Te, Po) and Li${}_3$O$B$ ($B$ = Cl, Br, I), which are the most energetically stable compounds, are dynamically stable cubic phases without imaginary phonon modes. However, Li${}_3$FS and Li${}_3$FSe, while energetically stable, are dynamically unstable at equilibrium and become dynamically stable under triaxial compressive strain. In addition, we report the electronic structure and density of states (DOS) of all compounds, which show a substantial change in band gap upon anion interchange. The strain engineering of the lithium chalcohalide family illustrates how a few percent of the strain can tune the electronic band gap within the electrochemical stability window for solid battery applications. This study unveils essential characteristics of the anion site-interchange mechanism and provides a foundation for the understanding and design of lithium chalcohalide antiperovskites.