DOE OSTI2020
Li3V6O13 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are three inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to five O2- atoms to form LiO5 square pyramids that share a cornercorner with one VO6 octahedra, corners with two equivalent LiO5 square pyramids, edges with four VO6 octahedra, and an edgeedge with one LiO5 square pyramid. The corner-sharing octahedral tilt angles are 8°. There are a spread of Li–O bond distances ranging from 1.99–2.14 Å. In the second Li1+ site, Li1+ is bonded to five O2- atoms to form LiO5 square pyramids that share a cornercorner with one VO6 octahedra, corners with two equivalent LiO5 square pyramids, edges with four VO6 octahedra, and an edgeedge with one LiO5 square pyramid. The corner-sharing octahedral tilt angles are 8°. There are a spread of Li–O bond distances ranging from 1.99–2.15 Å. In the third Li1+ site, Li1+ is bonded in a square co-planar geometry to four O2- atoms. There are a spread of Li–O bond distances ranging from 2.01–2.21 Å. There are six inequivalent V+3.83+ sites. In the first V+3.83+ site, V+3.83+ is bonded to six O2- atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedra tilt angles range from 0–15°. There are a spread of V–O bond distances ranging from 1.97–2.03 Å. In the second V+3.83+ site, V+3.83+ is bonded to six O2- atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedra tilt angles range from 0–11°. There are a spread of V–O bond distances ranging from 1.84–2.04 Å. In the third V+3.83+ site, V+3.83+ is bonded to six O2- atoms to form distorted VO6 octahedra that share corners with three VO6 octahedra, a cornercorner with one LiO5 square pyramid, an edgeedge with one VO6 octahedra, and edges with four LiO5 square pyramids. The corner-sharing octahedra tilt angles range from 8–18°. There are a spread of V–O bond distances ranging from 1.71–2.18 Å. In the fourth V+3.83+ site, V+3.83+ is bonded to six O2- atoms to form distorted VO6 octahedra that share corners with three VO6 octahedra, a cornercorner with one LiO5 square pyramid, an edgeedge with one VO6 octahedra, and edges with four LiO5 square pyramids. The corner-sharing octahedra tilt angles range from 4–18°. There are a spread of V–O bond distances ranging from 1.70–2.17 Å. In the fifth V+3.83+ site, V+3.83+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of V–O bond distances ranging from 1.68–2.35 Å. In the sixth V+3.83+ site, V+3.83+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of V–O bond distances ranging from 1.69–2.36 Å. There are thirteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a square co-planar geometry to one Li1+ and three V+3.83+ atoms. In the second O2- site, O2- is bonded in a square co-planar geometry to one Li1+ and three V+3.83+ atoms. In the third O2- site, O2- is bonded to two Li1+ and three V+3.83+ atoms to form OLi2V3 square pyramids that share corners with two equivalent OLi2V3 square pyramids, corners with two OLiV4 trigonal bipyramids, an edgeedge with one OLi2V3 square pyramid, and edges with seven OLiV4 trigonal bipyramids. In the fourth O2- site, O2- is bonded to two Li1+ and three V+3.83+ atoms to form OLi2V3 square pyramids that share corners with two equivalent OLi2V3 square pyramids, corners with two OLiV4 trigonal bipyramids, an edgeedge with one OLi2V3 square pyramid, and edges with seven OLiV4 trigonal bipyramids. In the fifth O2- site, O2- is bonded to one Li1+ and four V+3.83+ atoms to form distorted OLiV4 trigonal bipyramids that share a cornercorner with one OLi2V3 square pyramid, corners with three OLiV4 trigonal bipyramids, edges with three OLi2V3 square pyramids, and edges with five OLiV4 trigonal bipyramids. In the sixth O2- site, O2- is bonded to one Li1+ and four V+3.83+ atoms to form distorted OLiV4 trigonal bipyramids that share a cornercorner with one OLi2V3 square pyramid, corners with three OLiV4 trigonal bipyramids, edges with three OLi2V3 square pyramids, and edges with five OLiV4 trigonal bipyramids. In the seventh O2- site, O2- is bonded in a square co-planar geometry to two equivalent Li1+ and two V+3.83+ atoms. In the eighth O2- site, O2- is bonded in a linear geometry to two V+3.83+ atoms. In the ninth O2- site, O2- is bonded in a linear geometry to two V+3.83+ atoms. In the tenth O2- site, O2- is bonded in a linear geometry to two V+3.83+ atoms. In the eleventh O2- site, O2- is bonded in a linear geometry to two V+3.83+ atoms. In the twelfth O2- site, O2- is bonded to two equivalent Li1+ and three V+3.83+ atoms to form OLi2V3 trigonal bipyramids that share a cornercorner with one OLi2V3 square pyramid, corners with three OLiV4 trigonal bipyramids, edges with four OLi2V3 square pyramids, and edges with four OLiV4 trigonal bipyramids. In the thirteenth O2- site, O2- is bonded to two equivalent Li1+ and three V+3.83+ atoms to form OLi2V3 trigonal bipyramids that share a cornercorner with one OLi2V3 square pyramid, corners with three OLiV4 trigonal bipyramids, edges with four OLi2V3 square pyramids, and edges with four OLiV4 trigonal bipyramids.