Materials Data on Li4Mn5O12 by Materials Project

Abstract

Li4Mn5O12 is Spinel-like structured and crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are eight inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with two equivalent LiO6 octahedra and corners with ten MnO6 octahedra. The corner-sharing octahedra tilt angles range from 57–64°. There are a spread of Li–O bond distances ranging from 1.94–2.03 Å. In the second Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with two equivalent LiO6 octahedra and corners with ten MnO6 octahedra. The corner-sharing octahedra tilt angles range from 57–63°. There are a spread of Li–O bond distances ranging from 1.94–2.01 Å. In the third Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with two LiO6 octahedra and corners with ten MnO6 octahedra. The corner-sharing octahedra tilt angles range from 55–65°. There are a spread of Li–O bond distances ranging from 1.94–2.00 Å. In the fourth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with two LiO6 octahedra and corners with ten MnO6 octahedra. The corner-sharing octahedra tilt angles range from 54–66°. There is two shorter (1.93 Å) and two longer (1.99 Å) Li–O bond length. In the fifth Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Li–O bond distances ranging from 2.06–2.10 Å. In the sixth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with two equivalent LiO6 octahedra and corners with ten MnO6 octahedra. The corner-sharing octahedra tilt angles range from 57–64°. There are a spread of Li–O bond distances ranging from 1.95–2.02 Å. In the seventh Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with two equivalent LiO6 octahedra and corners with ten MnO6 octahedra. The corner-sharing octahedra tilt angles range from 57–63°. There are a spread of Li–O bond distances ranging from 1.94–2.03 Å. In the eighth Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Li–O bond distances ranging from 2.06–2.11 Å. There are ten inequivalent Mn4+ sites. In the first Mn4+ site, Mn4+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra, an edgeedge with one LiO6 octahedra, and edges with five MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.87–1.98 Å. In the second Mn4+ site, Mn4+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra, an edgeedge with one LiO6 octahedra, and edges with five MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.86–2.03 Å. In the third Mn4+ site, Mn4+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra, an edgeedge with one LiO6 octahedra, and edges with five MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.87–1.98 Å. In the fourth Mn4+ site, Mn4+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra, edges with two equivalent LiO6 octahedra, and edges with four MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.92–1.96 Å. In the fifth Mn4+ site, Mn4+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra, an edgeedge with one LiO6 octahedra, and edges with five MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.86–2.02 Å. In the sixth Mn4+ site, Mn4+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra, an edgeedge with one LiO6 octahedra, and edges with five MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.87–1.98 Å. In the seventh Mn4+ site, Mn4+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra, an edgeedge with one LiO6 octahedra, and edges with five MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.86–2.02 Å. In the eighth Mn4+ site, Mn4+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra, an edgeedge with one LiO6 octahedra, and edges with five MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.86–2.02 Å. In the ninth Mn4+ site, Mn4+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra, an edgeedge with one LiO6 octahedra, and edges with five MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.87–1.98 Å. In the tenth Mn4+ site, Mn4+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra, edges with two equivalent LiO6 octahedra, and edges with four MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.92–1.97 Å. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded to one Li1+ and three Mn4+ atoms to form distorted OLiMn3 tetrahedra that share a cornercorner with one OLiMn3 tetrahedra, corners with six OLi2Mn2 trigonal pyramids, and edges with three OLiMn3 tetrahedra. In the second O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Li1+ and two Mn4+ atoms. In the third O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Li1+ and two Mn4+ atoms. In the fourth O2- site, O2- is bonded to one Li1+ and three Mn4+ atoms to form distorted OLiMn3 trigonal pyramids that share corners with six OLiMn3 tetrahedra, corners with three OLiMn3 trigonal pyramids, and an edgeedge with one OLi2Mn2 trigonal pyramid. In the fifth O2- site, O2- is bonded to two Li1+ and two Mn4+ atoms to form distorted OLi2Mn2 trigonal pyramids that share corners with five OLiMn3 tetrahedra, corners with three OLi2Mn2 trigonal pyramids, and an edgeedge with one OLiMn3 trigonal pyramid. In the sixth O2- site, O2- is bonded to one Li1+ and three Mn4+ atoms to form distorted OLiMn3 tetrahedra that share a cornercorner with one OLiMn3 tetrahedra, corners with seven OLi2Mn2 trigonal pyramids, and edges with three OLiMn3 tetrahedra. In the seventh O2- site, O2- is bonded to one Li1+ and three Mn4+ atoms to form distorted OLiMn3 trigonal pyramids that share corners with six OLiMn3 tetrahedra, corners with three OLi2Mn2 trigonal pyramids, and edges with two OLi2Mn2 trigonal pyramids. In the eighth O2- site, O2- is bonded to two Li1+ and two Mn4+ atoms to form distorted OLi2Mn2 trigonal pyramids that share corners with five OLiMn3 tetrahedra, corners with four OLi2Mn2 trigonal pyramids, and edges with two OLiMn3 trigonal pyramids. In the ninth O2- site, O2- is bonded to one Li1+ and three Mn4+ atoms to form distorted OLiMn3 tetrahedra that share a cornercorner with one OLiMn3 tetrahedra, corners with six OLi2Mn2 trigonal pyramids, and edges with three OLiMn3 tetrahedra. In the tenth O2- site, O2- is bonded to two Li1+ and two Mn4+ atoms to form distorted OLi2Mn2 trigonal pyramids that share corners with five OLiMn3 tetrahedra, corners with four OLi2Mn2 trigonal pyramids, and edges with two OLiMn3 trigonal pyramids. In the eleventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Li1+ and two Mn4+ atoms. In the twelfth O2- site, O2- is bonded to one Li1+ and three Mn4+ atoms to form distorted OLiMn3 tetrahedra that share a cornercorner with one OLiMn3 tetrahedra, corners with six OLi2Mn2 trigonal pyramids, and edges with three OLiMn3 tetrahedra. In the thirteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Li1+ and two Mn4+ atoms. In the fourteenth O2- site, O2- is bonded to one Li1+ and three Mn4+ atoms to form distorted OLiMn3 tetrahedra that share a cornercorner with one OLiMn3 tetrahedra, corners with six OLi2Mn2 trigonal pyramids, and edges with three OLiMn3 tetrahedra. In the fifteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Li1+ and two Mn4+ atoms. In the sixteenth O2- site, O2- is bonded to one Li1+ and three Mn4+ atoms to form a mixture of distorted edge and corner-sharing OLiMn3 tetrahedra. In the seventeenth O2- site, O2- is bonded to two Li1+ and two Mn4+ atoms to form a mixture of distorted edge and corner-sharing OLi2Mn2 trigonal pyramids. In the eighteenth O2- site, O2- is bonded to one Li1+ and three Mn4+ atoms to form distorted OLiMn3 trigonal pyramids that share corners with six OLiMn3 tetrahedra, corners with four OLiMn3 trigonal pyramids, and an edgeedge with one OLi2Mn2 trigonal pyramid. In the nineteenth O2- site, O2- is bonded to one Li1+ and three Mn4+ atoms to form distorted OLiMn3 tetrahedra that share a cornercorner with one OLiMn3 tetrahedra, corners with seven OLi2Mn2 trigonal pyramids, and edges with three OLiMn3 tetrahedra. In the twentieth O2- site, O2- is bonded to two Li1+ and two Mn4+ atoms to form a mixture of distorted edge and corner-sharing OLi2Mn2 trigonal pyramids. In the twenty-first O2- site, O2- is bonded to one Li1+ and three Mn4+ atoms to form distorted OLiMn3 trigonal pyramids that share corners with six OLiMn3 tetrahedra, corners with three OLi2Mn2 trigonal pyramids, and an edgeedge with one OLi2Mn2 trigonal pyramid. In the twenty-second O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Li1+ and two Mn4+ atoms. In the twenty-third O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Li1+ and two Mn4+ atoms. In the twenty-fourth O2- site, O2- is bonded to one Li1+ and three Mn4+ atoms to form distorted OLiMn3 tetrahedra that share a cornercorner with one OLiMn3 tetrahedra, corners with six OLi2Mn2 trigonal pyramids, and edges with three OLiMn3 tetrahedra.