DOE OSTI2020
Li2ZnCl4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are two inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to six Cl1- atoms to form LiCl6 octahedra that share corners with four equivalent LiCl6 octahedra, corners with two equivalent ZnCl4 tetrahedra, edges with four LiCl6 octahedra, and edges with two equivalent ZnCl4 tetrahedra. The corner-sharing octahedra tilt angles range from 50–54°. There are a spread of Li–Cl bond distances ranging from 2.56–2.64 Å. In the second Li1+ site, Li1+ is bonded to six Cl1- atoms to form LiCl6 octahedra that share corners with eight LiCl6 octahedra, corners with four equivalent ZnCl4 tetrahedra, edges with two equivalent LiCl6 octahedra, and an edgeedge with one ZnCl4 tetrahedra. The corner-sharing octahedra tilt angles range from 48–54°. There are a spread of Li–Cl bond distances ranging from 2.55–2.75 Å. Zn2+ is bonded to four Cl1- atoms to form ZnCl4 tetrahedra that share corners with six LiCl6 octahedra and edges with three LiCl6 octahedra. The corner-sharing octahedra tilt angles range from 59–63°. There are a spread of Zn–Cl bond distances ranging from 2.26–2.32 Å. There are three inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a rectangular see-saw-like geometry to three Li1+ and one Zn2+ atom. In the second Cl1- site, Cl1- is bonded to three Li1+ and one Zn2+ atom to form distorted corner-sharing ClLi3Zn trigonal pyramids. In the third Cl1- site, Cl1- is bonded in a rectangular see-saw-like geometry to three Li1+ and one Zn2+ atom.