Materials Data on Li5Mn8Fe11O32 by Materials Project

Li5Mn8Fe11O32 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are five inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with six MnO6 octahedra and corners with six FeO6 octahedra. The corner-sharing octahedra tilt angles range from 55–61°. There are a spread of Li–O bond distances ranging from 2.00–2.12 Å. In the second Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with six MnO6 octahedra and corners with six FeO6 octahedra. The corner-sharing octahedra tilt angles range from 56–61°. There are a spread of Li–O bond distances ranging from 2.00–2.07 Å. In the third Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with six MnO6 octahedra and corners with six FeO6 octahedra. The corner-sharing octahedra tilt angles range from 56–62°. There are a spread of Li–O bond distances ranging from 1.95–2.09 Å. In the fourth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with six MnO6 octahedra and corners with six FeO6 octahedra. The corner-sharing octahedra tilt angles range from 53–62°. There are a spread of Li–O bond distances ranging from 1.95–2.03 Å. In the fifth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with six MnO6 octahedra and corners with six FeO6 octahedra. The corner-sharing octahedra tilt angles range from 57–61°. There are a spread of Li–O bond distances ranging from 1.96–2.07 Å. There are eight inequivalent Mn+3.25+ sites. In the first Mn+3.25+ site, Mn+3.25+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with two FeO4 tetrahedra, corners with four LiO4 tetrahedra, edges with two MnO6 octahedra, and edges with four equivalent FeO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.94–2.02 Å. In the second Mn+3.25+ site, Mn+3.25+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with three equivalent LiO4 tetrahedra, corners with three equivalent FeO4 tetrahedra, edges with two MnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.90–2.16 Å. In the third Mn+3.25+ site, Mn+3.25+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with two equivalent FeO4 tetrahedra, corners with four LiO4 tetrahedra, edges with two MnO6 octahedra, and edges with four equivalent FeO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.94–1.97 Å. In the fourth Mn+3.25+ site, Mn+3.25+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with three equivalent LiO4 tetrahedra, corners with three equivalent FeO4 tetrahedra, edges with two MnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.93–2.13 Å. In the fifth Mn+3.25+ site, Mn+3.25+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with two equivalent FeO4 tetrahedra, corners with four LiO4 tetrahedra, edges with two MnO6 octahedra, and edges with four equivalent FeO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.92–2.14 Å. In the sixth Mn+3.25+ site, Mn+3.25+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra, edges with two MnO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.93–1.99 Å. In the seventh Mn+3.25+ site, Mn+3.25+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with three equivalent LiO4 tetrahedra, corners with three equivalent FeO4 tetrahedra, edges with two MnO6 octahedra, and edges with four FeO6 octahedra. All Mn–O bond lengths are 1.96 Å. In the eighth Mn+3.25+ site, Mn+3.25+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with three LiO4 tetrahedra, corners with three FeO4 tetrahedra, edges with two MnO6 octahedra, and edges with four equivalent FeO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.93–2.15 Å. There are seven inequivalent Fe3+ sites. In the first Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with two FeO4 tetrahedra, corners with four LiO4 tetrahedra, edges with two equivalent FeO6 octahedra, and edges with four MnO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.01–2.12 Å. In the second Fe3+ site, Fe3+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with six MnO6 octahedra and corners with six FeO6 octahedra. The corner-sharing octahedra tilt angles range from 55–63°. There are a spread of Fe–O bond distances ranging from 2.00–2.06 Å. In the third Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with two equivalent FeO4 tetrahedra, corners with four LiO4 tetrahedra, edges with two equivalent FeO6 octahedra, and edges with four MnO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.01–2.10 Å. In the fourth Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with two equivalent FeO4 tetrahedra, corners with four LiO4 tetrahedra, edges with two equivalent FeO6 octahedra, and edges with four MnO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.02–2.07 Å. In the fifth Fe3+ site, Fe3+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with six MnO6 octahedra and corners with six FeO6 octahedra. The corner-sharing octahedra tilt angles range from 54–62°. There are a spread of Fe–O bond distances ranging from 2.02–2.07 Å. In the sixth Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with three LiO4 tetrahedra, corners with three FeO4 tetrahedra, edges with two equivalent FeO6 octahedra, and edges with four MnO6 octahedra. There are a spread of Fe–O bond distances ranging from 1.99–2.14 Å. In the seventh Fe3+ site, Fe3+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with six MnO6 octahedra and corners with six FeO6 octahedra. The corner-sharing octahedra tilt angles range from 56–60°. There are a spread of Fe–O bond distances ranging from 1.91–1.95 Å. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, two Mn+3.25+, and one Fe3+ atom. In the second O2- site, O2- is bonded to one Mn+3.25+ and three Fe3+ atoms to form a mixture of distorted edge and corner-sharing OMnFe3 tetrahedra. In the third O2- site, O2- is bonded to one Mn+3.25+ and three Fe3+ atoms to form distorted OMnFe3 trigonal pyramids that share corners with three OMnFe3 tetrahedra and an edgeedge with one OLiMnFe2 trigonal pyramid. In the fourth O2- site, O2- is bonded to one Li1+, one Mn+3.25+, and two equivalent Fe3+ atoms to form distorted OLiMnFe2 trigonal pyramids that share corners with two equivalent OLiMnFe2 tetrahedra, corners with two OLiMnFe2 trigonal pyramids, and an edgeedge with one OMnFe3 trigonal pyramid. In the fifth O2- site, O2- is bonded to one Li1+, one Mn+3.25+, and two equivalent Fe3+ atoms to form distorted OLiMnFe2 trigonal pyramids that share corners with six OMnFe3 tetrahedra and an edgeedge with one OLiMnFe2 trigonal pyramid. In the sixth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Mn+3.25+ and three Fe3+ atoms. In the seventh O2- site, O2- is bonded to one Li1+, one Mn+3.25+, and two equivalent Fe3+ atoms to form distorted corner-sharing OLiMnFe2 tetrahedra. In the eighth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, two Mn+3.25+, and one Fe3+ atom. In the ninth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, two Mn+3.25+, and one Fe3+ atom. In the tenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Mn+3.25+ and two Fe3+ atoms. In the eleventh O2- site, O2- is bonded to one Li1+, one Mn+3.25+, and two equivalent Fe3+ atoms to form a mixture of distorted edge and corner-sharing OLiMnFe2 trigonal pyramids. In the twelfth O2- site, O2- is bonded to one Li1+, one Mn+3.25+, and two equivalent Fe3+ atoms to form distorted OLiMnFe2 tetrahedra that share corners with six OLiMnFe2 trigonal pyramids and an edgeedge with one OMnFe3 tetrahedra. In the thirteenth O2- site, O2- is bonded to one Li1+, one Mn+3.25+, and two equivalent Fe3+ atoms to form distorted OLiMnFe2 tetrahedra that share corners with six OLiMnFe2 trigonal pyramids and an edgeedge with one OMnFe3 trigonal pyramid. In the fourteenth O2- site, O2- is bonded to one Li1+, one Mn+3.25+, and two equivalent Fe3+ atoms to form a mixture of distorted edge and corner-sharing OLiMnFe2 trigonal pyramids. In the fifteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Mn+3.25+ and two Fe3+ atoms. In the sixteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, two Mn+3.25+, and one Fe3+ atom. In the seventeenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, two Mn+3.25+, and one Fe3+ atom. In the eighteenth O2- site, O2- is bonded to one Li1+, one Mn+3.25+, and two equivalent Fe3+ atoms to form distorted OLiMnFe2 trigonal pyramids that share corners with two equivalent OMnFe3 tetrahedra, corners with four OLiMnFe2 trigonal pyramids, and an edgeedge with one OLiMnFe2 trigonal pyramid. In the nineteenth O2- site, O2- is bonded to one Li1+, one Mn+3.25+, and two equivalent Fe3+ atoms to form distorted OLiMnFe2 trigonal pyramids that share corners with three equivalent OMnFe3 tetrahedra, corners with three OMnFe3 trigonal pyramids, and an edgeedge with one OLiMnFe2 trigonal pyramid. In the twentieth O2- site, O2- is bonded to one Li1+, one Mn+3.25+, and two equivalent Fe3+ atoms to form a mixture of distorted edge and corner-sharing OLiMnFe2 trigonal pyramids. In the twenty-first O2- site, O2- is bonded to one Mn+3.25+ and three Fe3+ atoms to form distorted OMnFe3 tetrahedra that share corners with six OLiMnFe2 trigonal pyramids and an edgeedge with one OMnFe3 trigonal pyramid. In the twenty-second O2- site, O2- is bonded to one Mn+3.25+ and three Fe3+ atoms to form distorted OMnFe3 trigonal pyramids that share corners with five OLiMnFe2 trigonal pyramids and an edgeedge with one OMnFe3 tetrahedra. In the twenty-third O2- site, O2- is bonded to one Mn+3.25+ and three Fe3+ atoms to form distorted OMnFe3 trigonal pyramids that share a cornercorner with one OMnFe3 tetrahedra, corners with five OLiMnFe2 trigonal pyramids, and an edgeedge with one OLiMnFe2 tetrahedra. In the twenty-fourth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Mn+3.25+ and two Fe3+ atoms.

Li₅Mn₈Fe₁₁O₃₂为尖晶石衍生结构，结晶于单斜晶系Cm空间群，其结构为三维网状。该晶体存在5个不等价的Li⁺位点。在第一个Li⁺位点中，Li⁺与4个O²⁻原子配位，形成LiO₄四面体，该四面体与6个MnO₆八面体及6个FeO₆八面体通过顶角相连。共顶八面体的倾斜角范围为55°~61°，Li–O键长分布于2.00~2.12 Å之间。在第二个Li⁺位点中，Li⁺与4个O²⁻原子配位，形成LiO₄四面体，该四面体与6个MnO₆八面体及6个FeO₆八面体通过顶角相连。共顶八面体的倾斜角范围为56°~61°，Li–O键长分布于2.00~2.07 Å之间。在第三个Li⁺位点中，Li⁺与4个O²⁻原子配位，形成LiO₄四面体，该四面体与6个MnO₆八面体及6个FeO₆八面体通过顶角相连。共顶八面体的倾斜角范围为56°~62°，Li–O键长分布于1.95~2.09 Å之间。在第四个Li⁺位点中，Li⁺与4个O²⁻原子配位，形成LiO₄四面体，该四面体与6个MnO₆八面体及6个FeO₆八面体通过顶角相连。共顶八面体的倾斜角范围为53°~62°，Li–O键长分布于1.95~2.03 Å之间。在第五个Li⁺位点中，Li⁺与4个O²⁻原子配位，形成LiO₄四面体，该四面体与6个MnO₆八面体及6个FeO₆八面体通过顶角相连。共顶八面体的倾斜角范围为57°~61°，Li–O键长分布于1.96~2.07 Å之间。该晶体存在8个不等价的Mn³.²⁺位点。在第一个Mn³.²⁺位点中，Mn³.²⁺与6个O²⁻原子配位，形成MnO₆八面体，该八面体与2个FeO₄四面体、4个LiO₄四面体通过顶角相连，与2个MnO₆八面体、4个等价FeO₆八面体通过棱边相连。Mn–O键长分布于1.94~2.02 Å之间。在第二个Mn³.²⁺位点中，Mn³.²⁺与6个O²⁻原子配位，形成MnO₆八面体，该八面体与3个等价LiO₄四面体、3个等价FeO₄四面体通过顶角相连，与2个MnO₆八面体、4个FeO₆八面体通过棱边相连。Mn–O键长分布于1.90~2.16 Å之间。在第三个Mn³.²⁺位点中，Mn³.²⁺与6个O²⁻原子配位，形成MnO₆八面体，该八面体与2个等价FeO₄四面体、4个LiO₄四面体通过顶角相连，与2个MnO₆八面体、4个等价FeO₆八面体通过棱边相连。Mn–O键长分布于1.94~1.97 Å之间。在第四个Mn³.²⁺位点中，Mn³.²⁺与6个O²⁻原子配位，形成MnO₆八面体，该八面体与3个等价LiO₄四面体、3个等价FeO₄四面体通过顶角相连，与2个MnO₆八面体、4个FeO₆八面体通过棱边相连。Mn–O键长分布于1.93~2.13 Å之间。在第五个Mn³.²⁺位点中，Mn³.²⁺与6个O²⁻原子配位，形成MnO₆八面体，该八面体与2个等价FeO₄四面体、4个LiO₄四面体通过顶角相连，与2个MnO₆八面体、4个等价FeO₆八面体通过棱边相连。Mn–O键长分布于1.92~2.14 Å之间。在第六个Mn³.²⁺位点中，Mn³.²⁺与6个O²⁻原子配位，形成MnO₆八面体，该八面体与6个LiO₄四面体通过顶角相连，与2个MnO₆八面体、4个FeO₆八面体通过棱边相连。Mn–O键长分布于1.93~1.99 Å之间。在第七个Mn³.²⁺位点中，Mn³.²⁺与6个O²⁻原子配位，形成MnO₆八面体，该八面体与3个等价LiO₄四面体、3个等价FeO₄四面体通过顶角相连，与2个MnO₆八面体、4个FeO₆八面体通过棱边相连。所有Mn–O键长均为1.96 Å。在第八个Mn³.²⁺位点中，Mn³.²⁺与6个O²⁻原子配位，形成MnO₆八面体，该八面体与3个LiO₄四面体、3个FeO₄四面体通过顶角相连，与2个MnO₆八面体、4个等价FeO₆八面体通过棱边相连。Mn–O键长分布于1.93~2.15 Å之间。该晶体存在7个不等价的Fe³⁺位点。在第一个Fe³⁺位点中，Fe³⁺与6个O²⁻原子配位，形成FeO₆八面体，该八面体与2个FeO₄四面体、4个LiO₄四面体通过顶角相连，与2个等价FeO₆八面体、4个MnO₆八面体通过棱边相连。Fe–O键长分布于2.01~2.12 Å之间。在第二个Fe³⁺位点中，Fe³⁺与4个O²⁻原子配位，形成FeO₄四面体，该四面体与6个MnO₆八面体及6个FeO₆八面体通过顶角相连。共顶八面体的倾斜角范围为55°~63°，Fe–O键长分布于2.00~2.06 Å之间。在第三个Fe³⁺位点中，Fe³⁺与6个O²⁻原子配位，形成FeO₆八面体，该八面体与2个等价FeO₄四面体、4个LiO₄四面体通过顶角相连，与2个等价FeO₆八面体、4个MnO₆八面体通过棱边相连。Fe–O键长分布于2.01~2.10 Å之间。在第四个Fe³⁺位点中，Fe³⁺与6个O²⁻原子配位，形成FeO₆八面体，该八面体与2个等价FeO₄四面体、4个LiO₄四面体通过顶角相连，与2个等价FeO₆八面体、4个MnO₆八面体通过棱边相连。Fe–O键长分布于2.02~2.07 Å之间。在第五个Fe³⁺位点中，Fe³⁺与4个O²⁻原子配位，形成FeO₄四面体，该四面体与6个MnO₆八面体及6个FeO₆八面体通过顶角相连。共顶八面体的倾斜角范围为54°~62°，Fe–O键长分布于2.02~2.07 Å之间。在第六个Fe³⁺位点中，Fe³⁺与6个O²⁻原子配位，形成FeO₆八面体，该八面体与3个LiO₄四面体、3个FeO₄四面体通过顶角相连，与2个等价FeO₆八面体、4个MnO₆八面体通过棱边相连。Fe–O键长分布于1.99~2.14 Å之间。在第七个Fe³⁺位点中，Fe³⁺与4个O²⁻原子配位，形成FeO₄四面体，该四面体与6个MnO₆八面体及6个FeO₆八面体通过顶角相连。共顶八面体的倾斜角范围为56°~60°，Fe–O键长分布于1.91~1.95 Å之间。该晶体存在24个不等价的O²⁻位点。在第一个O²⁻位点中，O²⁻以矩形跷跷板状配位几何与1个Li⁺、2个Mn³.²⁺及1个Fe³⁺原子结合。在第二个O²⁻位点中，O²⁻与1个Mn³.²⁺及3个Fe³⁺原子结合，形成兼具畸变棱边共享与顶角共享特征的OMnFe₃四面体。在第三个O²⁻位点中，O²⁻与1个Mn³.²⁺及3个Fe³⁺原子结合，形成畸变OMnFe₃三角锥，该三角锥与3个OMnFe₃四面体通过顶角相连，并与1个OLiMnFe₂三角锥通过棱边相连。在第四个O²⁻位点中，O²⁻与1个Li⁺、1个Mn³.²⁺及2个等价Fe³⁺原子结合，形成畸变OLiMnFe₂三角锥，该三角锥与2个等价OLiMnFe₂四面体、2个OLiMnFe₂三角锥通过顶角相连，并与1个OMnFe₃三角锥通过棱边相连。在第五个O²⁻位点中，O²⁻与1个Li⁺、1个Mn³.²⁺及2个等价Fe³⁺原子结合，形成畸变OLiMnFe₂三角锥，该三角锥与6个OMnFe₃四面体通过顶角相连，并与1个OLiMnFe₂三角锥通过棱边相连。在第六个O²⁻位点中，O²⁻以畸变矩形跷跷板状配位几何与1个Mn³.²⁺及3个Fe³⁺原子结合。在第七个O²⁻位点中，O²⁻与1个Li⁺、1个Mn³.²⁺及2个等价Fe³⁺原子结合，形成畸变顶角共享的OLiMnFe₂四面体。在第八个O²⁻位点中，O²⁻以畸变矩形跷跷板状配位几何与1个Li⁺、2个Mn³.²⁺及1个Fe³⁺原子结合。在第九个O²⁻位点中，O²⁻以畸变矩形跷跷板状配位几何与1个Li⁺、2个Mn³.²⁺及1个Fe³⁺原子结合。在第十个O²⁻位点中，O²⁻以畸变矩形跷跷板状配位几何与2个Mn³.²⁺及2个Fe³⁺原子结合。在第十一个O²⁻位点中，O²⁻与1个Li⁺、1个Mn³.²⁺及2个等价Fe³⁺原子结合，形成兼具畸变棱边共享与顶角共享特征的OLiMnFe₂三角锥。在第十二个O²⁻位点中，O²⁻与1个Li⁺、1个Mn³.²⁺及2个等价Fe³⁺原子结合，形成畸变OLiMnFe₂四面体，该四面体与6个OLiMnFe₂三角锥通过顶角相连，并与1个OMnFe₃四面体通过棱边相连。在第十三个O²⁻位点中，O²⁻与1个Li⁺、1个Mn³.²⁺及2个等价Fe³⁺原子结合，形成畸变OLiMnFe₂四面体，该四面体与6个OLiMnFe₂三角锥通过顶角相连，并与1个OMnFe₃三角锥通过棱边相连。在第十四个O²⁻位点中，O²⁻与1个Li⁺、1个Mn³.²⁺及2个等价Fe³⁺原子结合，形成兼具畸变棱边共享与顶角共享特征的OLiMnFe₂三角锥。在第十五个O²⁻位点中，O²⁻以畸变矩形跷跷板状配位几何与2个Mn³.²⁺及2个Fe³⁺原子结合。在第十六个O²⁻位点中，O²⁻以矩形跷跷板状配位几何与1个Li⁺、2个Mn³.²⁺及1个Fe³⁺原子结合。在第十七个O²⁻位点中，O²⁻以矩形跷跷板状配位几何与1个Li⁺、2个Mn³.²⁺及1个Fe³⁺原子结合。在第十八个O²⁻位点中，O²⁻与1个Li⁺、1个Mn³.²⁺及2个等价Fe³⁺原子结合，形成畸变OLiMnFe₂三角锥，该三角锥与2个等价OMnFe₃四面体、4个OLiMnFe₂三角锥通过顶角相连，并与1个OLiMnFe₂三角锥通过棱边相连。在第十九个O²⁻位点中，O²⁻与1个Li⁺、1个Mn³.²⁺及2个等价Fe³⁺原子结合，形成畸变OLiMnFe₂三角锥，该三角锥与3个等价OMnFe₃四面体、3个OMnFe₃三角锥通过顶角相连，并与1个OLiMnFe₂三角锥通过棱边相连。在第二十个O²⁻位点中，O²⁻与1个Li⁺、1个Mn³.²⁺及2个等价Fe³⁺原子结合，形成兼具畸变棱边共享与顶角共享特征的OLiMnFe₂三角锥。在第二十一个O²⁻位点中，O²⁻与1个Mn³.²⁺及3个Fe³⁺原子结合，形成畸变OMnFe₃四面体，该四面体与6个OLiMnFe₂三角锥通过顶角相连，并与1个OMnFe₃三角锥通过棱边相连。在第二十二个O²⁻位点中，O²⁻与1个Mn³.²⁺及3个Fe³⁺原子结合，形成畸变OMnFe₃三角锥，该三角锥与5个OLiMnFe₂三角锥通过顶角相连，并与1个OMnFe₃四面体通过棱边相连。在第二十三个O²⁻位点中，O²⁻与1个Mn³.²⁺及3个Fe³⁺原子结合，形成畸变OMnFe₃三角锥，该三角锥与1个OMnFe₃四面体通过顶角相连，与5个OLiMnFe₂三角锥通过顶角相连，并与1个OLiMnFe₂四面体通过棱边相连。在第二十四个O²⁻位点中，O²⁻以畸变矩形跷跷板状配位几何与2个Mn³.²⁺及2个Fe³⁺原子结合。