Local Redox Reaction of High Valence Manganese in Li2MnO3-Based Lithium Battery Cathodes
Summary: Li2MnO3 endows Li-rich layered oxides with a superior energy density; however, its electron transfer mechanism is still unclear. Here, the electronic and thermodynamic behavior of LixMnO3 (x = 0.5–2) is determined using first-principles computations. The cationic redox, anionic redox, and l...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
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Elsevier
2020-05-01
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| Series: | Cell Reports Physical Science |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2666386420300552 |
| _version_ | 1818266674856460288 |
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| author | Zihe Zhang Shu Zhao Boya Wang Haijun Yu |
| author_facet | Zihe Zhang Shu Zhao Boya Wang Haijun Yu |
| author_sort | Zihe Zhang |
| collection | DOAJ |
| description | Summary: Li2MnO3 endows Li-rich layered oxides with a superior energy density; however, its electron transfer mechanism is still unclear. Here, the electronic and thermodynamic behavior of LixMnO3 (x = 0.5–2) is determined using first-principles computations. The cationic redox, anionic redox, and local electron exchange in Mn-O polyhedron are revealed. An obvious electron donation inclination of manganese is demonstrated when the Li+ content is low. Through ab initio molecular dynamics, high valence Mn6+ and Mn7+ are generated in the form of MnO4 tetrahedrons with structural transformation toward a disordered structure, controlled by the Li+ content and dynamic energy barrier. Furthermore, a local redox reaction between Mn6+ or Mn7+ and their surrounding oxygen atoms is elucidated. Consequently, a comprehensive understanding regarding the electron transfer in LixMnO3 is provided. Our results bring insight regarding the electron transfer mechanism in Li-rich layered oxide cathode materials and encourage further reconsideration and investigation into its redox mechanism. |
| first_indexed | 2024-12-12T20:10:28Z |
| format | Article |
| id | doaj.art-3c3cb5c0e43d4f03b01042bd60ff5189 |
| institution | Directory Open Access Journal |
| issn | 2666-3864 |
| language | English |
| last_indexed | 2024-12-12T20:10:28Z |
| publishDate | 2020-05-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Cell Reports Physical Science |
| spelling | doaj.art-3c3cb5c0e43d4f03b01042bd60ff51892022-12-22T00:13:31ZengElsevierCell Reports Physical Science2666-38642020-05-0115100061Local Redox Reaction of High Valence Manganese in Li2MnO3-Based Lithium Battery CathodesZihe Zhang0Shu Zhao1Boya Wang2Haijun Yu3College of Materials Science & Engineering, Key Laboratory of Advanced Functional Materials, Ministry of Education, Beijing University of Technology, Beijing 100124, ChinaCollege of Materials Science & Engineering, Key Laboratory of Advanced Functional Materials, Ministry of Education, Beijing University of Technology, Beijing 100124, ChinaCollege of Materials Science & Engineering, Key Laboratory of Advanced Functional Materials, Ministry of Education, Beijing University of Technology, Beijing 100124, ChinaCollege of Materials Science & Engineering, Key Laboratory of Advanced Functional Materials, Ministry of Education, Beijing University of Technology, Beijing 100124, China; Corresponding authorSummary: Li2MnO3 endows Li-rich layered oxides with a superior energy density; however, its electron transfer mechanism is still unclear. Here, the electronic and thermodynamic behavior of LixMnO3 (x = 0.5–2) is determined using first-principles computations. The cationic redox, anionic redox, and local electron exchange in Mn-O polyhedron are revealed. An obvious electron donation inclination of manganese is demonstrated when the Li+ content is low. Through ab initio molecular dynamics, high valence Mn6+ and Mn7+ are generated in the form of MnO4 tetrahedrons with structural transformation toward a disordered structure, controlled by the Li+ content and dynamic energy barrier. Furthermore, a local redox reaction between Mn6+ or Mn7+ and their surrounding oxygen atoms is elucidated. Consequently, a comprehensive understanding regarding the electron transfer in LixMnO3 is provided. Our results bring insight regarding the electron transfer mechanism in Li-rich layered oxide cathode materials and encourage further reconsideration and investigation into its redox mechanism.http://www.sciencedirect.com/science/article/pii/S2666386420300552Li-rich layered oxideslocal redox reactionfirst-principles computationLi-ion battery |
| spellingShingle | Zihe Zhang Shu Zhao Boya Wang Haijun Yu Local Redox Reaction of High Valence Manganese in Li2MnO3-Based Lithium Battery Cathodes Cell Reports Physical Science Li-rich layered oxides local redox reaction first-principles computation Li-ion battery |
| title | Local Redox Reaction of High Valence Manganese in Li2MnO3-Based Lithium Battery Cathodes |
| title_full | Local Redox Reaction of High Valence Manganese in Li2MnO3-Based Lithium Battery Cathodes |
| title_fullStr | Local Redox Reaction of High Valence Manganese in Li2MnO3-Based Lithium Battery Cathodes |
| title_full_unstemmed | Local Redox Reaction of High Valence Manganese in Li2MnO3-Based Lithium Battery Cathodes |
| title_short | Local Redox Reaction of High Valence Manganese in Li2MnO3-Based Lithium Battery Cathodes |
| title_sort | local redox reaction of high valence manganese in li2mno3 based lithium battery cathodes |
| topic | Li-rich layered oxides local redox reaction first-principles computation Li-ion battery |
| url | http://www.sciencedirect.com/science/article/pii/S2666386420300552 |
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