Materials Data on LiCoOF2 by Materials Project

Abstract

LiCoOF2 crystallizes in the monoclinic Pc space group. The structure is three-dimensional. there are four inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to four F1- atoms to form LiF4 tetrahedra that share corners with three LiO2F4 octahedra, corners with three CoOF5 octahedra, and corners with two equivalent LiOF3 tetrahedra. The corner-sharing octahedra tilt angles range from 55–66°. There are a spread of Li–F bond distances ranging from 1.86–1.90 Å. In the second Li1+ site, Li1+ is bonded to two O2- and four F1- atoms to form LiO2F4 octahedra that share a cornercorner with one CoO2F4 octahedra, corners with three LiF4 tetrahedra, corners with two equivalent CoO4F trigonal bipyramids, edges with two equivalent LiO2F4 octahedra, and edges with three CoO2F4 octahedra. The corner-sharing octahedral tilt angles are 8°. There are one shorter (2.08 Å) and one longer (2.11 Å) Li–O bond lengths. There are a spread of Li–F bond distances ranging from 1.95–2.33 Å. In the third Li1+ site, Li1+ is bonded to one O2- and three F1- atoms to form LiOF3 tetrahedra that share corners with two equivalent CoOF5 octahedra, corners with three LiO2F4 octahedra, corners with two equivalent LiF4 tetrahedra, and a cornercorner with one CoO4F trigonal bipyramid. The corner-sharing octahedra tilt angles range from 51–74°. The Li–O bond length is 2.02 Å. There is two shorter (1.87 Å) and one longer (1.92 Å) Li–F bond length. In the fourth Li1+ site, Li1+ is bonded to two O2- and four F1- atoms to form distorted LiO2F4 octahedra that share a cornercorner with one CoO2F4 octahedra, corners with three LiF4 tetrahedra, corners with two equivalent CoO4F trigonal bipyramids, edges with two equivalent LiO2F4 octahedra, and edges with two CoOF5 octahedra. The corner-sharing octahedral tilt angles are 56°. There are one shorter (2.19 Å) and one longer (2.30 Å) Li–O bond lengths. There are a spread of Li–F bond distances ranging from 1.99–2.11 Å. There are four inequivalent Co3+ sites. In the first Co3+ site, Co3+ is bonded in a 5-coordinate geometry to two O2- and three F1- atoms. There is one shorter (1.79 Å) and one longer (1.87 Å) Co–O bond length. There are a spread of Co–F bond distances ranging from 1.96–2.08 Å. In the second Co3+ site, Co3+ is bonded to four O2- and one F1- atom to form distorted CoO4F trigonal bipyramids that share corners with three CoOF5 octahedra, corners with four LiO2F4 octahedra, a cornercorner with one LiOF3 tetrahedra, and an edgeedge with one CoO2F4 octahedra. The corner-sharing octahedra tilt angles range from 23–73°. There are a spread of Co–O bond distances ranging from 1.78–1.95 Å. The Co–F bond length is 2.10 Å. In the third Co3+ site, Co3+ is bonded to one O2- and five F1- atoms to form CoOF5 octahedra that share a cornercorner with one CoO2F4 octahedra, corners with four LiF4 tetrahedra, corners with two equivalent CoO4F trigonal bipyramids, an edgeedge with one CoO2F4 octahedra, and edges with three LiO2F4 octahedra. The corner-sharing octahedral tilt angles are 58°. The Co–O bond length is 1.75 Å. There are a spread of Co–F bond distances ranging from 1.94–2.11 Å. In the fourth Co3+ site, Co3+ is bonded to two O2- and four F1- atoms to form CoO2F4 octahedra that share a cornercorner with one CoOF5 octahedra, corners with two LiO2F4 octahedra, a cornercorner with one LiF4 tetrahedra, a cornercorner with one CoO4F trigonal bipyramid, an edgeedge with one CoOF5 octahedra, edges with two LiO2F4 octahedra, and an edgeedge with one CoO4F trigonal bipyramid. The corner-sharing octahedra tilt angles range from 8–58°. There is one shorter (1.81 Å) and one longer (1.88 Å) Co–O bond length. There are a spread of Co–F bond distances ranging from 1.99–2.20 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded to two Li1+ and two Co3+ atoms to form OLi2Co2 tetrahedra that share corners with two equivalent FLi3Co tetrahedra and an edgeedge with one FLi3Co tetrahedra. In the second O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+ and two Co3+ atoms. In the third O2- site, O2- is bonded in a distorted trigonal planar geometry to three Co3+ atoms. In the fourth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+ and two Co3+ atoms. There are eight inequivalent F1- sites. In the first F1- site, F1- is bonded to three Li1+ and one Co3+ atom to form distorted FLi3Co tetrahedra that share corners with two equivalent OLi2Co2 tetrahedra, corners with two equivalent FLi3Co tetrahedra, and an edgeedge with one FLi2Co2 trigonal pyramid. In the second F1- site, F1- is bonded in a distorted trigonal planar geometry to one Li1+ and two Co3+ atoms. In the third F1- site, F1- is bonded in a trigonal planar geometry to two Li1+ and one Co3+ atom. In the fourth F1- site, F1- is bonded to three Li1+ and one Co3+ atom to form distorted FLi3Co tetrahedra that share corners with two equivalent FLi3Co tetrahedra, corners with two equivalent FLi2Co2 trigonal pyramids, and an edgeedge with one OLi2Co2 tetrahedra. In the fifth F1- site, F1- is bonded in a trigonal planar geometry to two Li1+ and one Co3+ atom. In the sixth F1- site, F1- is bonded to two Li1+ and two Co3+ atoms to form a mixture of distorted edge and corner-sharing FLi2Co2 trigonal pyramids. In the seventh F1- site, F1- is bonded in a distorted see-saw-like geometry to two Li1+ and two Co3+ atoms. In the eighth F1- site, F1- is bonded in a distorted trigonal planar geometry to three Co3+ atoms.