Comparison of small polaron migration and phase separation in olivine LiMnPO4 and LiFePO4 using hybrid density functional theory
Using hybrid density functional theory based on the Heyd-Scuseria-Ernzerhof (HSE06) functional, we compared polaron migration and phase separation in olivine LiMnPO[subscript 4] to LiFePO[subscript 4]. The barriers for free hole and electron polaron migration in the Mn olivine system are calculated...
| Principais autores: | , , |
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| Formato: | Artigo |
| Idioma: | en_US |
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American Physical Society
2011
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| Acesso em linha: | http://hdl.handle.net/1721.1/62839 |
| _version_ | 1826195974123421696 |
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| author | Ong, Shyue Ping Chevrier, Vincent L. Ceder, Gerbrand |
| author2 | Massachusetts Institute of Technology. Department of Materials Science and Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Materials Science and Engineering Ong, Shyue Ping Chevrier, Vincent L. Ceder, Gerbrand |
| author_sort | Ong, Shyue Ping |
| collection | MIT |
| description | Using hybrid density functional theory based on the Heyd-Scuseria-Ernzerhof (HSE06) functional, we compared polaron migration and phase separation in olivine LiMnPO[subscript 4] to LiFePO[subscript 4]. The barriers for free hole and electron polaron migration in the Mn olivine system are calculated to be 303 and 196 meV, respectively, significantly higher than the corresponding barriers of 170 and 133 meV, respectively, for the Fe olivine system, in agreement with previous experimental findings. These results suggest that the electronic conductivities of LiMnPO4 and MnPO4 are about 177 and 11 times lower than their respective Fe analogs at room temperature. In the presence of lithium vacancies or ions, the barriers for both hole and electron polaron migration were found to be about 100–120 meV higher in the Mn olivine. The HSE06 functional, with its more universal treatment of self-interaction error, was found to be essential to the proper localization of a polaron in the Mn olivine but predicted qualitatively incorrect phase separation behavior in the LixFePO[subscript 4] system. |
| first_indexed | 2024-09-23T10:18:48Z |
| format | Article |
| id | mit-1721.1/62839 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T10:18:48Z |
| publishDate | 2011 |
| publisher | American Physical Society |
| record_format | dspace |
| spelling | mit-1721.1/628392022-09-26T17:08:57Z Comparison of small polaron migration and phase separation in olivine LiMnPO4 and LiFePO4 using hybrid density functional theory Ong, Shyue Ping Chevrier, Vincent L. Ceder, Gerbrand Massachusetts Institute of Technology. Department of Materials Science and Engineering Ceder, Gerbrand Ong, Shyue Ping Chevrier, Vincent L. Ceder, Gerbrand Using hybrid density functional theory based on the Heyd-Scuseria-Ernzerhof (HSE06) functional, we compared polaron migration and phase separation in olivine LiMnPO[subscript 4] to LiFePO[subscript 4]. The barriers for free hole and electron polaron migration in the Mn olivine system are calculated to be 303 and 196 meV, respectively, significantly higher than the corresponding barriers of 170 and 133 meV, respectively, for the Fe olivine system, in agreement with previous experimental findings. These results suggest that the electronic conductivities of LiMnPO4 and MnPO4 are about 177 and 11 times lower than their respective Fe analogs at room temperature. In the presence of lithium vacancies or ions, the barriers for both hole and electron polaron migration were found to be about 100–120 meV higher in the Mn olivine. The HSE06 functional, with its more universal treatment of self-interaction error, was found to be essential to the proper localization of a polaron in the Mn olivine but predicted qualitatively incorrect phase separation behavior in the LixFePO[subscript 4] system. United States. Dept. of Energy (DE-FG02-96ER45571) United States. Dept. of Energy (Contract No. DE-AC02-05CH11231) 2011-05-19T13:17:18Z 2011-05-19T13:17:18Z 2011-02 2011-01 Article http://purl.org/eprint/type/JournalArticle 1098-0121 1550-235X http://hdl.handle.net/1721.1/62839 Ong, Shyue Ping, Vincent L. Chevrier, and Gerbrand Ceder. “Comparison of Small Polaron Migration and Phase Separation in Olivine LiMnPO_{4} and LiFePO_{4} Using Hybrid Density Functional Theory.” Physical Review B 83.7 (2011) : 075112. ©2011 American Physical Society en_US http://dx.doi.org/10.1103/PhysRevB.83.075112 Physical Review B Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Physical Society APS |
| spellingShingle | Ong, Shyue Ping Chevrier, Vincent L. Ceder, Gerbrand Comparison of small polaron migration and phase separation in olivine LiMnPO4 and LiFePO4 using hybrid density functional theory |
| title | Comparison of small polaron migration and phase separation in olivine LiMnPO4 and LiFePO4 using hybrid density functional theory |
| title_full | Comparison of small polaron migration and phase separation in olivine LiMnPO4 and LiFePO4 using hybrid density functional theory |
| title_fullStr | Comparison of small polaron migration and phase separation in olivine LiMnPO4 and LiFePO4 using hybrid density functional theory |
| title_full_unstemmed | Comparison of small polaron migration and phase separation in olivine LiMnPO4 and LiFePO4 using hybrid density functional theory |
| title_short | Comparison of small polaron migration and phase separation in olivine LiMnPO4 and LiFePO4 using hybrid density functional theory |
| title_sort | comparison of small polaron migration and phase separation in olivine limnpo4 and lifepo4 using hybrid density functional theory |
| url | http://hdl.handle.net/1721.1/62839 |
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