Materials Data on Li6Co6O5F11 by Materials Project

Li6Co6O5F11 is Spinel-derived structured and crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are six inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share a cornercorner with one LiOF5 octahedra and corners with eleven CoO3F3 octahedra. The corner-sharing octahedra tilt angles range from 50–58°. There are a spread of Li–O bond distances ranging from 1.95–2.02 Å. In the second Li1+ site, Li1+ is bonded to six F1- atoms to form LiF6 octahedra that share corners with six LiF4 tetrahedra, an edgeedge with one LiOF5 octahedra, and edges with five CoO3F3 octahedra. There are a spread of Li–F bond distances ranging from 2.00–2.20 Å. In the third Li1+ site, Li1+ is bonded to four F1- atoms to form LiF4 tetrahedra that share corners with four LiF6 octahedra and corners with eight CoO3F3 octahedra. The corner-sharing octahedra tilt angles range from 55–65°. There are a spread of Li–F bond distances ranging from 1.93–2.14 Å. In the fourth Li1+ site, Li1+ is bonded to one O2- and three F1- atoms to form LiOF3 tetrahedra that share corners with five LiF6 octahedra and corners with seven CoO3F3 octahedra. The corner-sharing octahedra tilt angles range from 52–62°. The Li–O bond length is 1.91 Å. There are a spread of Li–F bond distances ranging from 1.93–1.98 Å. In the fifth Li1+ site, Li1+ is bonded to one O2- and five F1- atoms to form LiOF5 octahedra that share corners with six LiO4 tetrahedra, an edgeedge with one LiF6 octahedra, and edges with five CoOF5 octahedra. The Li–O bond length is 2.12 Å. There are a spread of Li–F bond distances ranging from 2.06–2.12 Å. In the sixth Li1+ site, Li1+ is bonded to four F1- atoms to form LiF4 tetrahedra that share corners with two equivalent LiOF5 octahedra and corners with ten CoO3F3 octahedra. The corner-sharing octahedra tilt angles range from 57–67°. There are a spread of Li–F bond distances ranging from 1.95–2.01 Å. There are six inequivalent Co+2.50+ sites. In the first Co+2.50+ site, Co+2.50+ is bonded to three O2- and three F1- atoms to form CoO3F3 octahedra that share corners with six LiO4 tetrahedra, an edgeedge with one LiF6 octahedra, and edges with five CoO3F3 octahedra. There are two shorter (2.03 Å) and one longer (2.04 Å) Co–O bond lengths. There are two shorter (2.11 Å) and one longer (2.16 Å) Co–F bond lengths. In the second Co+2.50+ site, Co+2.50+ is bonded to three O2- and three F1- atoms to form CoO3F3 octahedra that share corners with six LiO4 tetrahedra, an edgeedge with one LiOF5 octahedra, and edges with five CoO3F3 octahedra. There are a spread of Co–O bond distances ranging from 1.89–1.93 Å. There are a spread of Co–F bond distances ranging from 2.19–2.25 Å. In the third Co+2.50+ site, Co+2.50+ is bonded to one O2- and five F1- atoms to form CoOF5 octahedra that share corners with six LiO4 tetrahedra, edges with three LiF6 octahedra, and edges with three CoOF5 octahedra. The Co–O bond length is 1.84 Å. There are a spread of Co–F bond distances ranging from 2.01–2.13 Å. In the fourth Co+2.50+ site, Co+2.50+ is bonded to three O2- and three F1- atoms to form CoO3F3 octahedra that share corners with six LiO4 tetrahedra, an edgeedge with one LiF6 octahedra, and edges with five CoO3F3 octahedra. There are a spread of Co–O bond distances ranging from 1.93–2.00 Å. There are a spread of Co–F bond distances ranging from 2.13–2.18 Å. In the fifth Co+2.50+ site, Co+2.50+ is bonded to three O2- and three F1- atoms to form CoO3F3 octahedra that share corners with six LiO4 tetrahedra, an edgeedge with one LiF6 octahedra, and edges with five CoO3F3 octahedra. There are a spread of Co–O bond distances ranging from 1.93–1.99 Å. There are a spread of Co–F bond distances ranging from 2.12–2.17 Å. In the sixth Co+2.50+ site, Co+2.50+ is bonded to one O2- and five F1- atoms to form CoOF5 octahedra that share corners with six LiO4 tetrahedra, edges with three LiF6 octahedra, and edges with three CoOF5 octahedra. The Co–O bond length is 1.88 Å. There are a spread of Co–F bond distances ranging from 2.01–2.14 Å. There are five inequivalent O2- sites. In the first O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+ and three Co+2.50+ atoms. In the second O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+ and three Co+2.50+ atoms. In the third O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+ and three Co+2.50+ atoms. In the fourth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Li1+ and two Co+2.50+ atoms. In the fifth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+ and three Co+2.50+ atoms. There are eleven inequivalent F1- sites. In the first F1- site, F1- is bonded in a 4-coordinate geometry to one Li1+ and three Co+2.50+ atoms. In the second F1- site, F1- is bonded to two Li1+ and two Co+2.50+ atoms to form a mixture of distorted corner and edge-sharing FLi2Co2 trigonal pyramids. In the third F1- site, F1- is bonded to two Li1+ and two Co+2.50+ atoms to form a mixture of distorted corner and edge-sharing FLi2Co2 trigonal pyramids. In the fourth F1- site, F1- is bonded in a rectangular see-saw-like geometry to three Li1+ and one Co+2.50+ atom. In the fifth F1- site, F1- is bonded in a rectangular see-saw-like geometry to three Li1+ and one Co+2.50+ atom. In the sixth F1- site, F1- is bonded in a rectangular see-saw-like geometry to two Li1+ and two Co+2.50+ atoms. In the seventh F1- site, F1- is bonded in a 4-coordinate geometry to one Li1+ and three Co+2.50+ atoms. In the eighth F1- site, F1- is bonded to two Li1+ and two Co+2.50+ atoms to form a mixture of distorted corner and edge-sharing FLi2Co2 tetrahedra. In the ninth F1- site, F1- is bonded to two Li1+ and two Co+2.50+ atoms to form a mixture of distorted corner and edge-sharing FLi2Co2 trigonal pyramids. In the tenth F1- site, F1- is bonded to two Li1+ and two Co+2.50+ atoms to form a mixture of distorted corner and edge-sharing FLi2Co2 tetrahedra. In the eleventh F1- site, F1- is bonded to two Li1+ and two Co+2.50+ atoms to form a mixture of distorted corner and edge-sharing FLi2Co2 tetrahedra.Li₆Co₆O₅F₁₁ 源自尖晶石结构，结晶于三斜晶系P1空间群，其晶体结构为三维无限框架。该体系存在6个不等价的Li⁺配位位点： 1. 第一个Li⁺位点：Li⁺与4个O²⁻配位形成LiO₄四面体，该四面体与1个LiOF₅八面体共享1个顶点，同时与11个CoO₃F₃八面体共享多个顶点；共顶八面体的倾斜角介于50~58°之间，Li–O键长分布范围为1.95~2.02 Å。 2. 第二个Li⁺位点：Li⁺与6个F⁻配位形成LiF₆八面体，该八面体与6个LiF₄四面体共享顶点、与1个LiOF₅八面体共享1条边，同时与5个CoO₃F₃八面体共享多条边；Li–F键长分布范围为2.00~2.20 Å。 3. 第三个Li⁺位点：Li⁺与4个F⁻配位形成LiF₄四面体，该四面体与4个LiF₆八面体共享顶点，同时与8个CoO₃F₃八面体共享顶点；共顶八面体的倾斜角介于55~65°之间，Li–F键长分布范围为1.93~2.14 Å。 4. 第四个Li⁺位点：Li⁺与1个O²⁻和3个F⁻配位形成LiOF₃四面体，该四面体与5个LiF₆八面体共享顶点，同时与7个CoO₃F₃八面体共享顶点；共顶八面体的倾斜角介于52~62°之间，Li–O键长为1.91 Å，Li–F键长分布范围为1.93~1.98 Å。 5. 第五个Li⁺位点：Li⁺与1个O²⁻和5个F⁻配位形成LiOF₅八面体，该八面体与6个LiO₄四面体共享顶点、与1个LiF₆八面体共享1条边，同时与5个CoOF₅八面体共享多条边；Li–O键长为2.12 Å，Li–F键长分布范围为2.06~2.12 Å。 6. 第六个Li⁺位点：Li⁺与4个F⁻配位形成LiF₄四面体，该四面体与2个等价的LiOF₅八面体共享顶点，同时与10个CoO₃F₃八面体共享顶点；共顶八面体的倾斜角介于57~67°之间，Li–F键长分布范围为1.95~2.01 Å。 该体系存在6个不等价的Co²⁺（平均氧化态为+2.5）配位位点： 1. 第一个Co²⁺位点：Co²⁺与3个O²⁻和3个F⁻配位形成CoO₃F₃八面体，该八面体与6个LiO₄四面体共享顶点、与1个LiF₆八面体共享1条边，同时与5个CoO₃F₃八面体共享多条边；Co–O键长存在2个较短的2.03 Å和1个较长的2.04 Å，Co–F键长存在2个较短的2.11 Å和1个较长的2.16 Å。 2. 第二个Co²⁺位点：Co²⁺与3个O²⁻和3个F⁻配位形成CoO₃F₃八面体，该八面体与6个LiO₄四面体共享顶点、与1个LiOF₅八面体共享1条边，同时与5个CoO₃F₃八面体共享多条边；Co–O键长分布范围为1.89~1.93 Å，Co–F键长分布范围为2.19~2.25 Å。 3. 第三个Co²⁺位点：Co²⁺与1个O²⁻和5个F⁻配位形成CoOF₅八面体，该八面体与6个LiO₄四面体共享顶点、与3个LiF₆八面体共享边，同时与3个CoOF₅八面体共享边；Co–O键长为1.84 Å，Co–F键长分布范围为2.01~2.13 Å。 4. 第四个Co²⁺位点：Co²⁺与3个O²⁻和3个F⁻配位形成CoO₃F₃八面体，该八面体与6个LiO₄四面体共享顶点、与1个LiF₆八面体共享1条边，同时与5个CoO₃F₃八面体共享多条边；Co–O键长分布范围为1.93~2.00 Å，Co–F键长分布范围为2.13~2.18 Å。 5. 第五个Co²⁺位点：Co²⁺与3个O²⁻和3个F⁻配位形成CoO₃F₃八面体，该八面体与6个LiO₄四面体共享顶点、与1个LiF₆八面体共享1条边，同时与5个CoO₃F₃八面体共享多条边；Co–O键长分布范围为1.93~1.99 Å，Co–F键长分布范围为2.12~2.17 Å。 6. 第六个Co²⁺位点：Co²⁺与1个O²⁻和5个F⁻配位形成CoOF₅八面体，该八面体与6个LiO₄四面体共享顶点、与3个LiF₆八面体共享边，同时与3个CoOF₅八面体共享边；Co–O键长为1.88 Å，Co–F键长分布范围为2.01~2.14 Å。 该体系存在5个不等价的O²⁻配位位点： 1. 第一个O²⁻位点：O²⁻以矩形跷跷板型配位几何构型与1个Li⁺和3个Co²⁺结合。 2. 第二个O²⁻位点：O²⁻以矩形跷跷板型配位几何构型与1个Li⁺和3个Co²⁺结合。 3. 第三个O²⁻位点：O²⁻以矩形跷跷板型配位几何构型与1个Li⁺和3个Co²⁺结合。 4. 第四个O²⁻位点：O²⁻以矩形跷跷板型配位几何构型与2个Li⁺和2个Co²⁺结合。 5. 第五个O²⁻位点：O²⁻以矩形跷跷板型配位几何构型与1个Li⁺和3个Co²⁺结合。 该体系存在11个不等价的F⁻配位位点： 1. 第一个F⁻位点：F⁻以四配位几何构型与1个Li⁺和3个Co²⁺结合。 2. 第二个F⁻位点：F⁻与2个Li⁺和2个Co²⁺结合，形成兼具畸变共顶和共边的FLi₂Co₂三角锥结构基元。 3. 第三个F⁻位点：F⁻与2个Li⁺和2个Co²⁺结合，形成兼具畸变共顶和共边的FLi₂Co₂三角锥结构基元。 4. 第四个F⁻位点：F⁻以矩形跷跷板型配位几何构型与3个Li⁺和1个Co²⁺结合。 5. 第五个F⁻位点：F⁻以矩形跷跷板型配位几何构型与3个Li⁺和1个Co²⁺结合。 6. 第六个F⁻位点：F⁻以矩形跷跷板型配位几何构型与2个Li⁺和2个Co²⁺结合。 7. 第七个F⁻位点：F⁻以四配位几何构型与1个Li⁺和3个Co²⁺结合。 8. 第八个F⁻位点：F⁻与2个Li⁺和2个Co²⁺结合，形成兼具畸变共顶和共边的FLi₂Co₂四面体结构基元。 9. 第九个F⁻位点：F⁻与2个Li⁺和2个Co²⁺结合，形成兼具畸变共顶和共边的FLi₂Co₂三角锥结构基元。 10. 第十个F⁻位点：F⁻与2个Li⁺和2个Co²⁺结合，形成兼具畸变共顶和共边的FLi₂Co₂四面体结构基元。 11. 第十一个F⁻位点：F⁻与2个Li⁺和2个Co²⁺结合，形成兼具畸变共顶和共边的FLi₂Co₂四面体结构基元。