DOE OSTI2020
Li10Fe3Co3(NiO8)2 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are ten inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to four O2- atoms to form distorted LiO4 tetrahedra that share a cornercorner with one FeO6 octahedra, corners with two CoO6 octahedra, corners with three equivalent LiO6 octahedra, corners with three equivalent NiO6 octahedra, an edgeedge with one CoO6 octahedra, and edges with two FeO6 octahedra. The corner-sharing octahedra tilt angles range from 7–64°. There are a spread of Li–O bond distances ranging from 1.82–1.88 Å. In the second Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share a cornercorner with one CoO6 octahedra, corners with two FeO6 octahedra, corners with three equivalent LiO6 octahedra, corners with three equivalent NiO6 octahedra, an edgeedge with one FeO6 octahedra, and edges with two CoO6 octahedra. The corner-sharing octahedra tilt angles range from 7–61°. There is three shorter (1.81 Å) and one longer (1.89 Å) Li–O bond length. In the third Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 1.96–2.39 Å. In the fourth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 1.94–2.41 Å. In the fifth Li1+ site, Li1+ is bonded in a 3-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 1.95–2.50 Å. In the sixth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 1.93–2.36 Å. In the seventh Li1+ site, Li1+ is bonded in a 3-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 1.93–2.49 Å. In the eighth Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with three equivalent NiO6 octahedra, corners with three equivalent LiO4 tetrahedra, edges with two equivalent CoO6 octahedra, edges with four FeO6 octahedra, and a faceface with one NiO6 octahedra. The corner-sharing octahedra tilt angles range from 7–9°. There are a spread of Li–O bond distances ranging from 2.07–2.17 Å. In the ninth Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with three equivalent NiO6 octahedra, corners with three equivalent LiO4 tetrahedra, edges with two equivalent FeO6 octahedra, edges with four CoO6 octahedra, and a faceface with one NiO6 octahedra. The corner-sharing octahedra tilt angles range from 8–11°. There are a spread of Li–O bond distances ranging from 2.06–2.13 Å. In the tenth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 1.97–2.44 Å. There are three inequivalent Fe3+ sites. In the first Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with two equivalent NiO6 octahedra, a cornercorner with one LiO4 tetrahedra, an edgeedge with one NiO6 octahedra, edges with two equivalent LiO6 octahedra, edges with two equivalent FeO6 octahedra, edges with two equivalent CoO6 octahedra, and an edgeedge with one LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 48–51°. There are a spread of Fe–O bond distances ranging from 2.01–2.07 Å. In the second Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with two equivalent NiO6 octahedra, a cornercorner with one LiO4 tetrahedra, an edgeedge with one NiO6 octahedra, edges with two equivalent LiO6 octahedra, edges with two equivalent FeO6 octahedra, edges with two equivalent CoO6 octahedra, and an edgeedge with one LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 52–53°. There are a spread of Fe–O bond distances ranging from 2.02–2.07 Å. In the third Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with two equivalent NiO6 octahedra, a cornercorner with one LiO4 tetrahedra, an edgeedge with one NiO6 octahedra, edges with two equivalent LiO6 octahedra, edges with four CoO6 octahedra, and an edgeedge with one LiO4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. There are a spread of Fe–O bond distances ranging from 2.00–2.07 Å. There are three inequivalent Co3+ sites. In the first Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with two equivalent NiO6 octahedra, a cornercorner with one LiO4 tetrahedra, an edgeedge with one NiO6 octahedra, edges with two equivalent LiO6 octahedra, edges with four FeO6 octahedra, and an edgeedge with one LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 48–49°. There are a spread of Co–O bond distances ranging from 1.98–2.00 Å. In the second Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with two equivalent NiO6 octahedra, a cornercorner with one LiO4 tetrahedra, an edgeedge with one NiO6 octahedra, edges with two equivalent LiO6 octahedra, edges with two equivalent FeO6 octahedra, edges with two equivalent CoO6 octahedra, and an edgeedge with one LiO4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. There are a spread of Co–O bond distances ranging from 1.97–2.00 Å. In the third Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with two equivalent NiO6 octahedra, a cornercorner with one LiO4 tetrahedra, an edgeedge with one NiO6 octahedra, edges with two equivalent LiO6 octahedra, edges with two equivalent FeO6 octahedra, edges with two equivalent CoO6 octahedra, and an edgeedge with one LiO4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. There are a spread of Co–O bond distances ranging from 1.96–2.00 Å. There are two inequivalent Ni2+ sites. In the first Ni2+ site, Ni2+ is bonded to six O2- atoms to form NiO6 octahedra that share corners with two equivalent FeO6 octahedra, corners with three equivalent LiO6 octahedra, corners with four CoO6 octahedra, corners with three equivalent LiO4 tetrahedra, an edgeedge with one CoO6 octahedra, edges with two FeO6 octahedra, and a faceface with one LiO6 octahedra. The corner-sharing octahedra tilt angles range from 7–51°. There are a spread of Ni–O bond distances ranging from 2.09–2.22 Å. In the second Ni2+ site, Ni2+ is bonded to six O2- atoms to form NiO6 octahedra that share corners with two equivalent CoO6 octahedra, corners with three equivalent LiO6 octahedra, corners with four FeO6 octahedra, corners with three equivalent LiO4 tetrahedra, an edgeedge with one FeO6 octahedra, edges with two CoO6 octahedra, and a faceface with one LiO6 octahedra. The corner-sharing octahedra tilt angles range from 8–53°. There are a spread of Ni–O bond distances ranging from 2.09–2.20 Å. There are sixteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a 7-coordinate geometry to four Li1+, two Fe3+, and one Co3+ atom. In the second O2- site, O2- is bonded in a 7-coordinate geometry to four Li1+, one Fe3+, and two Co3+ atoms. In the third O2- site, O2- is bonded in a 7-coordinate geometry to four Li1+, two Co3+, and one Ni2+ atom. In the fourth O2- site, O2- is bonded in a 5-coordinate geometry to four Li1+, one Fe3+, one Co3+, and one Ni2+ atom. In the fifth O2- site, O2- is bonded to three Li1+, one Fe3+, one Co3+, and one Ni2+ atom to form OLi3FeCoNi octahedra that share edges with four OLi3FeCoNi octahedra and edges with two OLi3FeCo2 pentagonal pyramids. In the sixth O2- site, O2- is bonded to three Li1+, two Co3+, and one Ni2+ atom to form OLi3Co2Ni octahedra that share edges with four OLi3FeCoNi octahedra and edges with two OLi3FeCo2 pentagonal pyramids. In the seventh O2- site, O2- is bonded to three Li1+, one Fe3+, and two Co3+ atoms to form distorted edge-sharing OLi3FeCo2 pentagonal pyramids. In the eighth O2- site, O2- is bonded to three Li1+, two Fe3+, and one Co3+ atom to form distorted edge-sharing OLi3Fe2Co pentagonal pyramids. In the ninth O2- site, O2- is bonded to three Li1+, one Fe3+, one Co3+, and one Ni2+ atom to form OLi3FeCoNi octahedra that share edges with four OLi3FeCoNi octahedra and edges with two OLi3FeCo2 pentagonal pyramids. In the tenth O2- site, O2- is bonded to three Li1+, one Fe3+, one Co3+, and one Ni2+ atom to form OLi3FeCoNi octahedra that share edges with four OLi3Co2Ni octahedra and edges with two OLi3FeCo2 pentagonal pyramids. In the eleventh O2- site, O2- is bonded in a 7-coordinate geometry to four Li1+, one Fe3+, one Co3+, and one Ni2+ atom. In the twelfth O2- site, O2- is bonded in a 1-coordinate geometry to four Li1+, one Fe3+, one Co3+, and one Ni2+ atom. In the thirteenth O2- site, O2- is bonded to three Li1+, one Fe3+, one Co3+, and one Ni2+ atom to form OLi3FeCoNi octahedra that share edges with four OLi3Co2Ni octahedra and edges with two OLi3FeCo2 pentagonal pyramids. In the fourteenth O2- site, O2- is bonded to three Li1+, two Fe3+, and one Ni2+ atom to form OLi3Fe2Ni octahedra that share edges with four OLi3FeCoNi octahedra and edges with two OLi3FeCo2 pentagonal pyramids. In the fifteenth O2- site, O2- is bonded in a 1-coordinate geometry to four Li1+, two Fe3+, and one Ni2+ atom. In the sixteenth O2- site, O2- is bonded in a 7-coordinate geometry to four Li1+, one Fe3+, one Co3+, and one Ni2+ atom.