Materials Data on Li4Fe3Ni2Sb3O16 by Materials Project

Li4Fe3Ni2Sb3O16 is Hausmannite-derived structured and crystallizes in the monoclinic Cm 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 distorted LiO4 tetrahedra that share corners with three equivalent NiO6 octahedra, corners with four SbO6 octahedra, and corners with five FeO6 octahedra. The corner-sharing octahedra tilt angles range from 50–64°. There are a spread of Li–O bond distances ranging from 1.95–2.25 Å. In the second 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 1.77–2.06 Å. In the third 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 equivalent SbO6 octahedra, an edgeedge with one SbO6 octahedra, and edges with two equivalent FeO6 octahedra. The corner-sharing octahedra tilt angles range from 58–65°. There are a spread of Li–O bond distances ranging from 1.83–1.96 Å. In the fourth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with four FeO6 octahedra and corners with five SbO6 octahedra. The corner-sharing octahedra tilt angles range from 57–59°. There are a spread of Li–O bond distances ranging from 1.99–2.09 Å. There are two 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, corners with four LiO4 tetrahedra, and edges with four equivalent SbO6 octahedra. The corner-sharing octahedral tilt angles are 52°. There are a spread of Fe–O bond distances ranging from 2.03–2.10 Å. In the second Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with three LiO4 tetrahedra, an edgeedge with one NiO6 octahedra, edges with two equivalent FeO6 octahedra, edges with two equivalent SbO6 octahedra, and an edgeedge with one LiO4 tetrahedra. There are a spread of Fe–O bond distances ranging from 2.02–2.12 Å. There are two inequivalent Ni2+ sites. In the first Ni2+ site, Ni2+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Ni–O bond distances ranging from 1.99–2.42 Å. In the second Ni2+ site, Ni2+ is bonded to six O2- atoms to form NiO6 octahedra that share corners with two equivalent FeO6 octahedra, corners with four equivalent SbO6 octahedra, corners with three equivalent LiO4 tetrahedra, an edgeedge with one SbO6 octahedra, and edges with two equivalent FeO6 octahedra. The corner-sharing octahedra tilt angles range from 52–53°. There are a spread of Ni–O bond distances ranging from 2.04–2.37 Å. There are two inequivalent Sb5+ sites. In the first Sb5+ site, Sb5+ is bonded to six O2- atoms to form SbO6 octahedra that share corners with two equivalent NiO6 octahedra, corners with four LiO4 tetrahedra, edges with two equivalent FeO6 octahedra, and edges with two equivalent SbO6 octahedra. The corner-sharing octahedral tilt angles are 53°. There are a spread of Sb–O bond distances ranging from 1.97–2.06 Å. In the second Sb5+ site, Sb5+ is bonded to six O2- atoms to form SbO6 octahedra that share corners with three LiO4 tetrahedra, an edgeedge with one NiO6 octahedra, edges with four equivalent FeO6 octahedra, and an edgeedge with one LiO4 tetrahedra. There are a spread of Sb–O bond distances ranging from 2.01–2.03 Å. There are twelve inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one Fe3+, one Ni2+, and one Sb5+ atom. In the second O2- site, O2- is bonded in a 4-coordinate geometry to one Li1+, one Ni2+, and two equivalent Sb5+ atoms. In the third O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one Fe3+, and two equivalent Sb5+ atoms. In the fourth O2- site, O2- is bonded to one Li1+, one Fe3+, and two equivalent Sb5+ atoms to form a mixture of distorted corner and edge-sharing OLiFeSb2 tetrahedra. In the fifth O2- site, O2- is bonded to one Li1+, two equivalent Fe3+, and one Sb5+ atom to form distorted OLiFe2Sb tetrahedra that share corners with two equivalent OLiFe2Ni tetrahedra and corners with two equivalent OLiFeNiSb trigonal pyramids. In the sixth O2- site, O2- is bonded to one Li1+, one Fe3+, one Ni2+, and one Sb5+ atom to form distorted OLiFeNiSb tetrahedra that share corners with three OLiFeSb2 tetrahedra, corners with three equivalent OLiFeNiSb trigonal pyramids, and an edgeedge with one OLiFeNiSb tetrahedra. In the seventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one Ni2+, and two equivalent Sb5+ atoms. In the eighth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, two equivalent Fe3+, and one Ni2+ atom. In the ninth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, one Fe3+, one Ni2+, and one Sb5+ atom. In the tenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, two equivalent Fe3+, and one Sb5+ atom. In the eleventh O2- site, O2- is bonded to one Li1+, one Fe3+, one Ni2+, and one Sb5+ atom to form distorted OLiFeNiSb trigonal pyramids that share corners with five OLiFe2Ni tetrahedra, a cornercorner with one OLiFeNiSb trigonal pyramid, an edgeedge with one OLiFeSb2 tetrahedra, and an edgeedge with one OLiFeNiSb trigonal pyramid. In the twelfth O2- site, O2- is bonded to one Li1+, two equivalent Fe3+, and one Ni2+ atom to form distorted OLiFe2Ni tetrahedra that share corners with two equivalent OLiFe2Sb tetrahedra and corners with two equivalent OLiFeNiSb trigonal pyramids.

Li₄Fe₃Ni₂Sb₃O₁₆为菱锰矿（Hausmannite）衍生结构，结晶于单斜晶系Cm空间群，整体为三维框架结构。体系中存在4个不等价的Li⁺位点。在第一个Li⁺位点中，Li⁺与4个O²⁻配位形成畸变LiO₄四面体（tetrahedra），该四面体分别与3个等价NiO₆八面体（octahedra）、4个等价SbO₆八面体以及5个FeO₆八面体通过共角相连，共角八面体的倾斜角范围为50°~64°，Li-O键长分布区间为1.95~2.25 Å。在第二个Li⁺位点中，Li⁺以矩形跷跷板型配位构型与4个O²⁻结合，Li-O键长分布区间为1.77~2.06 Å。在第三个Li⁺位点中，Li⁺与4个O²⁻配位形成畸变LiO₄四面体，该四面体与1个FeO₆八面体共角、2个等价SbO₆八面体共角、1个SbO₆八面体共边，同时与2个等价FeO₆八面体共边，共角八面体倾斜角范围为58°~65°，Li-O键长分布区间为1.83~1.96 Å。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4个FeO₆八面体、5个SbO₆八面体通过共角相连，共角八面体倾斜角范围为57°~59°，Li-O键长分布区间为1.99~2.09 Å。体系中存在2个不等价的Fe³+位点。在第一个Fe³+位点中，Fe³+与6个O²⁻配位形成FeO₆八面体，该八面体与2个等价NiO₆八面体共角、4个LiO₄四面体共角、4个等价SbO₆八面体共边，共角八面体倾斜角为52°，Fe-O键长分布区间为2.03~2.10 Å。在第二个Fe³+位点中，Fe³+与6个O²⁻配位形成FeO₆八面体，该八面体与3个LiO₄四面体共角、1个NiO₆八面体共边、2个等价FeO₆八面体共边、2个等价SbO₆八面体共边，同时与1个LiO₄四面体共边，Fe-O键长分布区间为2.02~2.12 Å。体系中存在2个不等价的Ni²+位点。在第一个Ni²+位点中，Ni²+以六配位构型与6个O²⁻结合，Ni-O键长分布区间为1.99~2.42 Å。在第二个Ni²+位点中，Ni²+与6个O²⁻配位形成NiO₆八面体，该八面体与2个等价FeO₆八面体共角、4个等价SbO₆八面体共角、3个等价LiO₄四面体共角、1个SbO₆八面体共边，同时与2个等价FeO₆八面体共边，共角八面体倾斜角范围为52°~53°，Ni-O键长分布区间为2.04~2.37 Å。体系中存在2个不等价的Sb⁵+位点。在第一个Sb⁵+位点中，Sb⁵+与6个O²⁻配位形成SbO₆八面体，该八面体与2个等价NiO₆八面体共角、4个LiO₄四面体共角、2个等价FeO₆八面体共边、2个等价SbO₆八面体共边，共角八面体倾斜角为53°，Sb-O键长分布区间为1.97~2.06 Å。在第二个Sb⁵+位点中，Sb⁵+与6个O²⁻配位形成SbO₆八面体，该八面体与3个LiO₄四面体共角、1个NiO₆八面体共边、4个等价FeO₆八面体共边，同时与1个LiO₄四面体共边，Sb-O键长分布区间为2.01~2.03 Å。体系中存在12个不等价的O²⁻位点。在第一个O²⁻位点中，O²⁻以畸变矩形跷跷板型配位构型与1个Li⁺、1个Fe³+、1个Ni²+以及1个Sb⁵+配位。在第二个O²⁻位点中，O²⁻以四配位构型与1个Li⁺、1个Ni²+以及2个等价Sb⁵+结合。在第三个O²⁻位点中，O²⁻以畸变矩形跷跷板型配位构型与1个Li⁺、1个Fe³+以及2个等价Sb⁵+配位。在第四个O²⁻位点中，O²⁻与1个Li⁺、1个Fe³+以及2个等价Sb⁵+结合，形成畸变共角与共边混合型OLiFeSb₂四面体。在第五个O²⁻位点中，O²⁻与1个Li⁺、2个等价Fe³+以及1个Sb⁵+结合，形成畸变OLiFe₂Sb四面体，该四面体与2个等价OLiFe₂Ni四面体共角，同时与2个等价OLiFeNiSb三角锥（trigonal pyramids）共角。在第六个O²⁻位点中，O²⁻与1个Li⁺、1个Fe³+、1个Ni²+以及1个Sb⁵+结合，形成畸变OLiFeNiSb四面体，该四面体与3个OLiFeSb₂四面体共角、3个等价OLiFeNiSb三角锥共角，同时与1个OLiFeNiSb四面体共边。在第七个O²⁻位点中，O²⁻以畸变矩形跷跷板型配位构型与1个Li⁺、1个Ni²+以及2个等价Sb⁵+配位。在第八个O²⁻位点中，O²⁻以畸变矩形跷跷板型配位构型与1个Li⁺、2个等价Fe³+以及1个Ni²+配位。在第九个O²⁻位点中，O²⁻以矩形跷跷板型配位构型与1个Li⁺、1个Fe³+、1个Ni²+以及1个Sb⁵+结合。在第十个O²⁻位点中，O²⁻以畸变矩形跷跷板型配位构型与1个Li⁺、2个等价Fe³+以及1个Sb⁵+配位。在第十一个O²⁻位点中，O²⁻与1个Li⁺、1个Fe³+、1个Ni²+以及1个Sb⁵+结合，形成畸变OLiFeNiSb三角锥，该三角锥与5个OLiFe₂Ni四面体共角、1个OLiFeNiSb三角锥共角，同时与1个OLiFeSb₂四面体共边、1个OLiFeNiSb三角锥共边。在第十二个O²⁻位点中，O²⁻与1个Li⁺、2个等价Fe³+以及1个Ni²+结合，形成畸变OLiFe₂Ni四面体，该四面体与2个等价OLiFe₂Sb四面体共角，同时与2个等价OLiFeNiSb三角锥共角。