DOI: 10.17188/1308362
title: Materials Data on Li4Co5O9F by Materials Project

description: Li4Co5O9F crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are four inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with six CoO6 octahedra, edges with six LiO6 octahedra, and edges with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 2–11°. There are a spread of Li–O bond distances ranging from 2.02–2.43 Å. In the second Li1+ site, Li1+ is bonded to five O2- and one F1- atom to form distorted LiO5F octahedra that share corners with six CoO6 octahedra, edges with four LiO5F octahedra, and edges with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 9–20°. There are a spread of Li–O bond distances ranging from 2.02–2.29 Å. The Li–F bond length is 1.94 Å. In the third Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share corners with six CoO6 octahedra, edges with four LiO6 octahedra, and edges with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 3–26°. There are a spread of Li–O bond distances ranging from 2.07–2.56 Å. In the fourth Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with six CoO6 octahedra, edges with six LiO6 octahedra, and edges with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 6–10°. There are a spread of Li–O bond distances ranging from 2.10–2.26 Å. There are five inequivalent Co3+ sites. In the first Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with five LiO6 octahedra, edges with six LiO5F octahedra, and edges with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 2–10°. There are a spread of Co–O bond distances ranging from 1.86–1.94 Å. In the second Co3+ site, Co3+ is bonded to five O2- and one F1- atom to form CoO5F octahedra that share corners with four LiO6 octahedra, edges with three equivalent LiO6 octahedra, and edges with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 4–17°. There are a spread of Co–O bond distances ranging from 1.91–2.19 Å. The Co–F bond length is 2.27 Å. In the third Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six LiO6 octahedra, edges with six LiO6 octahedra, and edges with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 3–10°. There are a spread of Co–O bond distances ranging from 1.97–2.08 Å. In the fourth Co3+ site, Co3+ is bonded to four O2- and two equivalent F1- atoms to form CoO4F2 octahedra that share corners with four LiO5F octahedra, edges with three equivalent LiO5F octahedra, and edges with six CoO6 octahedra. The corner-sharing octahedra tilt angles range from 6–26°. There are a spread of Co–O bond distances ranging from 2.00–2.22 Å. There are one shorter (2.12 Å) and one longer (2.13 Å) Co–F bond lengths. In the fifth Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with five LiO6 octahedra, edges with six LiO6 octahedra, and edges with six CoO5F octahedra. The corner-sharing octahedra tilt angles range from 6–11°. There are a spread of Co–O bond distances ranging from 1.92–2.16 Å. There are nine inequivalent O2- sites. In the first O2- site, O2- is bonded to three Li1+ and three Co3+ atoms to form OLi3Co3 octahedra that share corners with five OLi3Co3 octahedra, a cornercorner with one OLi2Co3 square pyramid, and edges with twelve OLi3Co3 octahedra. The corner-sharing octahedra tilt angles range from 5–6°. In the second O2- site, O2- is bonded to two equivalent Li1+ and three Co3+ atoms to form OLi2Co3 square pyramids that share corners with three OLi3Co3 octahedra, edges with five OLi3Co3 octahedra, and edges with two equivalent OLi2Co3 square pyramids. The corner-sharing octahedra tilt angles range from 3–14°. In the third O2- site, O2- is bonded to three Li1+ and three Co3+ atoms to form OLi3Co3 octahedra that share corners with three OLi3Co3 octahedra, corners with two equivalent OLi2Co3 square pyramids, edges with seven OLi3Co3 octahedra, and edges with three equivalent OLi2Co3 square pyramids. The corner-sharing octahedra tilt angles range from 3–5°. In the fourth O2- site, O2- is bonded to three Li1+ and three Co3+ atoms to form OLi3Co3 octahedra that share corners with five OLi3Co3 octahedra, edges with ten OLi3Co3 octahedra, and edges with two equivalent OLi2Co3 square pyramids. The corner-sharing octahedra tilt angles range from 2–5°. In the fifth O2- site, O2- is bonded to three Li1+ and three Co3+ atoms to form distorted OLi3Co3 octahedra that share corners with five OLi3Co3 octahedra, edges with ten OLi3Co3 octahedra, and edges with two equivalent OLi2Co3 square pyramids. The corner-sharing octahedra tilt angles range from 3–11°. In the sixth O2- site, O2- is bonded to three Li1+ and three Co3+ atoms to form OLi3Co3 octahedra that share corners with three OLi3Co3 octahedra, corners with two equivalent OLi2Co3 square pyramids, edges with seven OLi3Co3 octahedra, and edges with three equivalent OLi2Co3 square pyramids. The corner-sharing octahedra tilt angles range from 1–2°. In the seventh O2- site, O2- is bonded to two equivalent Li1+ and three Co3+ atoms to form OLi2Co3 square pyramids that share corners with three OLi3Co3 octahedra, edges with five OLi3Co3 octahedra, and edges with two equivalent OLi2Co3 square pyramids. The corner-sharing octahedra tilt angles range from 3–19°. In the eighth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+ and three Co3+ atoms. In the ninth O2- site, O2- is bonded to three Li1+ and three Co3+ atoms to form OLi3Co3 octahedra that share corners with five OLi3Co3 octahedra, a cornercorner with one OLi2Co3 square pyramid, and edges with twelve OLi3Co3 octahedra. The corner-sharing octahedra tilt angles range from 1–11°. F1- is bonded in a distorted rectangular see-saw-like geometry to one Li1+ and three Co3+ atoms.