Materials Data on Li4Ti2V3Cu3O16 by Materials Project

Li4Ti2V3Cu3O16 is Hausmannite-derived structured and 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 four O2- atoms to form LiO4 tetrahedra that share corners with four CuO6 octahedra and corners with five VO6 octahedra. The corner-sharing octahedra tilt angles range from 44–71°. There are a spread of Li–O bond distances ranging from 1.99–2.09 Å. In the second Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share a cornercorner with one CuO6 octahedra, corners with two VO6 octahedra, an edgeedge with one VO6 octahedra, and edges with two CuO6 octahedra. The corner-sharing octahedra tilt angles range from 62–66°. There are a spread of Li–O bond distances ranging from 1.87–1.98 Å. In the third Li1+ site, Li1+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Li–O bond distances ranging from 1.88–2.00 Å. In the fourth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with three equivalent TiO6 octahedra, corners with four VO6 octahedra, and corners with five CuO6 octahedra. The corner-sharing octahedra tilt angles range from 51–66°. There is three shorter (1.95 Å) and one longer (1.99 Å) Li–O bond length. There are two inequivalent Ti4+ sites. In the first Ti4+ site, Ti4+ is bonded to six O2- atoms to form distorted TiO6 octahedra that share corners with two equivalent CuO6 octahedra, corners with four VO6 octahedra, corners with three equivalent LiO4 tetrahedra, an edgeedge with one VO6 octahedra, and edges with two CuO6 octahedra. The corner-sharing octahedra tilt angles range from 50–55°. There are a spread of Ti–O bond distances ranging from 1.84–2.45 Å. In the second Ti4+ site, Ti4+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Ti–O bond distances ranging from 1.83–2.28 Å. There are three inequivalent V5+ sites. In the first V5+ site, V5+ is bonded to six O2- atoms to form VO6 octahedra that share corners with two equivalent TiO6 octahedra, corners with four LiO4 tetrahedra, edges with two equivalent VO6 octahedra, and edges with two equivalent CuO6 octahedra. The corner-sharing octahedra tilt angles range from 50–55°. There are a spread of V–O bond distances ranging from 1.79–2.05 Å. In the second V5+ site, V5+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three LiO4 tetrahedra, an edgeedge with one TiO6 octahedra, edges with four CuO6 octahedra, and an edgeedge with one LiO4 tetrahedra. There are a spread of V–O bond distances ranging from 1.77–2.14 Å. In the third V5+ site, V5+ is bonded to six O2- atoms to form VO6 octahedra that share corners with two equivalent TiO6 octahedra, corners with four LiO4 tetrahedra, edges with two equivalent VO6 octahedra, and edges with two equivalent CuO6 octahedra. The corner-sharing octahedra tilt angles range from 51–52°. There are a spread of V–O bond distances ranging from 1.75–2.18 Å. There are three inequivalent Cu+1.67+ sites. In the first Cu+1.67+ site, Cu+1.67+ is bonded to six O2- atoms to form distorted CuO6 octahedra that share corners with three LiO4 tetrahedra, an edgeedge with one TiO6 octahedra, edges with two equivalent VO6 octahedra, edges with two equivalent CuO6 octahedra, and an edgeedge with one LiO4 tetrahedra. There are a spread of Cu–O bond distances ranging from 1.92–2.44 Å. In the second Cu+1.67+ site, Cu+1.67+ is bonded to six O2- atoms to form distorted CuO6 octahedra that share corners with three LiO4 tetrahedra, an edgeedge with one TiO6 octahedra, edges with two equivalent VO6 octahedra, edges with two equivalent CuO6 octahedra, and an edgeedge with one LiO4 tetrahedra. There are a spread of Cu–O bond distances ranging from 1.92–2.43 Å. In the third Cu+1.67+ site, Cu+1.67+ is bonded to six O2- atoms to form CuO6 octahedra that share corners with two equivalent TiO6 octahedra, corners with four LiO4 tetrahedra, and edges with four VO6 octahedra. The corner-sharing octahedra tilt angles range from 50–52°. There are a spread of Cu–O bond distances ranging from 1.97–2.24 Å. There are sixteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, one Ti4+, one V5+, and one Cu+1.67+ atom. In the second O2- site, O2- is bonded to one Li1+, one Ti4+, and two Cu+1.67+ atoms to form a mixture of edge and corner-sharing OLiTiCu2 tetrahedra. In the third O2- site, O2- is bonded to one Li1+, one V5+, and two Cu+1.67+ atoms to form distorted OLiVCu2 tetrahedra that share corners with four OLiVCu2 tetrahedra and an edgeedge with one OLiTiCu2 tetrahedra. In the fourth O2- site, O2- is bonded to one Li1+, one V5+, and two Cu+1.67+ atoms to form corner-sharing OLiVCu2 tetrahedra. In the fifth O2- site, O2- is bonded to one Li1+, two V5+, and one Cu+1.67+ atom to form corner-sharing OLiV2Cu tetrahedra. In the sixth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, one Ti4+, one V5+, and one Cu+1.67+ atom. In the seventh O2- site, O2- is bonded in a 4-coordinate geometry to one Li1+, one Ti4+, one V5+, and one Cu+1.67+ atom. In the eighth O2- site, O2- is bonded in a 4-coordinate geometry to one Li1+, one Ti4+, one V5+, and one Cu+1.67+ atom. In the ninth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, one Ti4+, and two Cu+1.67+ atoms. In the tenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one Ti4+, and two V5+ atoms. In the eleventh O2- site, O2- is bonded to one Li1+, one Ti4+, one V5+, and one Cu+1.67+ atom to form distorted corner-sharing OLiTiVCu tetrahedra. In the twelfth O2- site, O2- is bonded in a 4-coordinate geometry to one Li1+, one Ti4+, one V5+, and one Cu+1.67+ atom. In the thirteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, two V5+, and one Cu+1.67+ atom. In the fourteenth O2- site, O2- is bonded in a 4-coordinate geometry to one Li1+, one Ti4+, one V5+, and one Cu+1.67+ atom. In the fifteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one Ti4+, and two V5+ atoms. In the sixteenth O2- site, O2- is bonded in a 4-coordinate geometry to one Li1+, one Ti4+, one V5+, and one Cu+1.67+ atom.

Li₄Ti₂V₃Cu₃O₁₆为黑锰矿（Hausmannite）衍生结构，结晶于三斜晶系P1空间群，整体为三维骨架结构。存在4种不等价Li⁺位点。在第一个Li⁺位点中，Li⁺与4个O²⁻配位形成LiO₄四面体，该四面体与4个CuO₆八面体以及5个VO₆八面体共享顶点。共顶点八面体的倾斜角范围为44°~71°，Li-O键长分布在1.99~2.09 Å之间。在第二个Li⁺位点中，Li⁺与4个O²⁻配位形成LiO₄四面体，该四面体与1个CuO₆八面体共享顶点、与2个VO₆八面体共享顶点，与1个VO₆八面体共享边，同时与2个CuO₆八面体共享边。共顶点八面体倾斜角范围为62°~66°，Li-O键长分布在1.87~1.98 Å之间。在第三个Li⁺位点中，Li⁺采用类矩形跷板式配位构型与4个O²⁻结合，Li-O键长分布在1.88~2.00 Å之间。在第四个Li⁺位点中，Li⁺与4个O²⁻配位形成LiO₄四面体，该四面体与3个等价的TiO₆八面体共享顶点、与4个VO₆八面体共享顶点，同时与5个CuO₆八面体共享顶点。共顶点八面体倾斜角范围为51°~66°，该位点存在3条较短（1.95 Å）与1条较长（1.99 Å）的Li-O键长。存在2种不等价Ti⁴+位点。在第一个Ti⁴+位点中，Ti⁴+与6个O²⁻配位形成畸变TiO₆八面体，该八面体与2个等价的CuO₆八面体共享顶点、与4个VO₆八面体共享顶点、与3个等价的LiO₄四面体共享顶点，与1个VO₆八面体共享边，同时与2个CuO₆八面体共享边。共顶点八面体倾斜角范围为50°~55°，Ti-O键长分布在1.84~2.45 Å之间。在第二个Ti⁴+位点中，Ti⁴+采用六配位构型与6个O²⁻结合，Ti-O键长分布在1.83~2.28 Å之间。存在3种不等价V⁵+位点。在第一个V⁵+位点中，V⁵+与6个O²⁻配位形成VO₆八面体，该八面体与2个等价的TiO₆八面体共享顶点、与4个LiO₄四面体共享顶点，与2个等价的VO₆八面体共享边，同时与2个等价的CuO₆八面体共享边。共顶点八面体倾斜角范围为50°~55°，V-O键长分布在1.79~2.05 Å之间。在第二个V⁵+位点中，V⁵+与6个O²⁻配位形成VO₆八面体，该八面体与3个LiO₄四面体共享顶点、与1个TiO₆八面体共享边，与4个CuO₆八面体共享边，同时与1个LiO₄四面体共享边，V-O键长分布在1.77~2.14 Å之间。在第三个V⁵+位点中，V⁵+与6个O²⁻配位形成VO₆八面体，该八面体与2个等价的TiO₆八面体共享顶点、与4个LiO₄四面体共享顶点，与2个等价的VO₆八面体共享边，同时与2个等价的CuO₆八面体共享边。共顶点八面体倾斜角范围为51°~52°，V-O键长分布在1.75~2.18 Å之间。存在3种不等价Cu^(+1.67+)位点。在第一个Cu^(+1.67+)位点中，Cu^(+1.67+)与6个O²⁻配位形成畸变CuO₆八面体，该八面体与3个LiO₄四面体共享顶点、与1个TiO₆八面体共享边，与2个等价的VO₆八面体共享边、与2个等价的CuO₆八面体共享边，同时与1个LiO₄四面体共享边。Cu-O键长分布在1.92~2.44 Å之间。在第二个Cu^(+1.67+)位点中，Cu^(+1.67+)与6个O²⁻配位形成畸变CuO₆八面体，该八面体与3个LiO₄四面体共享顶点、与1个TiO₆八面体共享边，与2个等价的VO₆八面体共享边、与2个等价的CuO₆八面体共享边，同时与1个LiO₄四面体共享边。Cu-O键长分布在1.92~2.43 Å之间。在第三个Cu^(+1.67+)位点中，Cu^(+1.67+)与6个O²⁻配位形成CuO₆八面体，该八面体与2个等价的TiO₆八面体共享顶点、与4个LiO₄四面体共享顶点，同时与4个VO₆八面体共享边。共顶点八面体倾斜角范围为50°~52°，Cu-O键长分布在1.97~2.24 Å之间。存在16种不等价O²⁻位点。在第一个O²⁻位点中，O²⁻采用类矩形跷板式配位构型结合1个Li⁺、1个Ti⁴+、1个V⁵+与1个Cu^(+1.67+)原子。在第二个O²⁻位点中，O²⁻与1个Li⁺、1个Ti⁴+以及2个Cu^(+1.67+)结合，形成兼具边共享与顶点共享的OLiTiCu₂四面体结构。在第三个O²⁻位点中，O²⁻与1个Li⁺、1个V⁵+以及2个Cu^(+1.67+)结合，形成畸变OLiVCu₂四面体结构，该结构与4个OLiVCu₂四面体共享顶点，并与1个OLiTiCu₂四面体共享边。在第四个O²⁻位点中，O²⁻与1个Li⁺、1个V⁵+以及2个Cu^(+1.67+)结合，形成仅共享顶点的OLiVCu₂四面体结构。在第五个O²⁻位点中，O²⁻与1个Li⁺、2个V⁵+以及1个Cu^(+1.67+)结合，形成共享顶点的OLiV₂Cu四面体结构。在第六个O²⁻位点中，O²⁻采用类矩形跷板式配位构型结合1个Li⁺、1个Ti⁴+、1个V⁵+与1个Cu^(+1.67+)原子。在第七个O²⁻位点中，O²⁻采用四配位构型结合1个Li⁺、1个Ti⁴+、1个V⁵+与1个Cu^(+1.67+)原子。在第八个O²⁻位点中，O²⁻采用四配位构型结合1个Li⁺、1个Ti⁴+、1个V⁵+与1个Cu^(+1.67+)原子。在第九个O²⁻位点中，O²⁻采用类矩形跷板式配位构型结合1个Li⁺、1个Ti⁴+与2个Cu^(+1.67+)原子。在第十个O²⁻位点中，O²⁻采用畸变类矩形跷板式配位构型结合1个Li⁺、1个Ti⁴+与2个V⁵+原子。在第十一个O²⁻位点中，O²⁻与1个Li⁺、1个Ti⁴+、1个V⁵+以及1个Cu^(+1.67+)结合，形成畸变共享顶点的OLiTiVCu四面体结构。在第十二个O²⁻位点中，O²⁻采用四配位构型结合1个Li⁺、1个Ti⁴+、1个V⁵+与1个Cu^(+1.67+)原子。在第十三个O²⁻位点中，O²⁻采用类矩形跷板式配位构型结合1个Li⁺、2个V⁵+与1个Cu^(+1.67+)原子。在第十四个O²⁻位点中，O²⁻采用四配位构型结合1个Li⁺、1个Ti⁴+、1个V⁵+与1个Cu^(+1.67+)原子。在第十五个O²⁻位点中，O²⁻采用畸变类矩形跷板式配位构型结合1个Li⁺、1个Ti⁴+与2个V⁵+原子。在第十六个O²⁻位点中，O²⁻采用四配位构型结合1个Li⁺、1个Ti⁴+、1个V⁵+与1个Cu^(+1.67+)原子。