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 LiMnPO₄ to LiFePO₄. The barriers for free hole and electron polaron migration in the Mn olivine system are calculated to be 303 and 196 meV, r...
| Main Authors: | , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | en_US |
| Published: |
American Physical Society
2012
|
| Online Access: | http://hdl.handle.net/1721.1/69945 |
| _version_ | 1811096354824388608 |
|---|---|
| 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 LiMnPO₄ to LiFePO₄. 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 LiₓFePO₄ system. |
| first_indexed | 2024-09-23T16:42:31Z |
| format | Article |
| id | mit-1721.1/69945 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T16:42:31Z |
| publishDate | 2012 |
| publisher | American Physical Society |
| record_format | dspace |
| spelling | mit-1721.1/699452022-09-29T20:54:25Z 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 Ceder, Gerbrand Ong, Shyue Ping Chevrier, Vincent L. Using hybrid density functional theory based on the Heyd-Scuseria-Ernzerhof (HSE06) functional, we compared polaron migration and phase separation in olivine LiMnPO₄ to LiFePO₄. 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 LiₓFePO₄ system. United States. Dept. of Energy (Contract No. DE-FG02-96ER45571) United States. Dept. of Energy (Office of Vehicle Technologies, Batteries for Advanced Transportation Technologies (BATT) Program), Contract No. DE-AC02-05CH11231) 2012-04-05T14:37:01Z 2012-04-05T14:37:01Z 2011-02 2011-01 Article http://purl.org/eprint/type/JournalArticle 1098-0121 1550-235X http://hdl.handle.net/1721.1/69945 Ong, Shyue Ping, Vincent L. Chevrier, and Gerbrand Ceder. “Comparison of Small Polaron Migration and Phase Separation in Olivine LiMnPO₄ and LiFePO₄ using Hybrid Density Functional Theory.” Physical Review B 83.7 (2011): [7 pages]. en_US http://dx.doi.org/10.1103/PhysRevB.83.075112 Physical Review B Creative Commons Attribution-Noncommercial-Share Alike 3.0 http://creativecommons.org/licenses/by-nc-sa/3.0/ application/pdf American Physical Society Prof. Ceder via Angie Locknar |
| 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/1721.1/69945 |
| work_keys_str_mv | AT ongshyueping comparisonofsmallpolaronmigrationandphaseseparationinolivinelimnpo4andlifepo4usinghybriddensityfunctionaltheory AT chevriervincentl comparisonofsmallpolaronmigrationandphaseseparationinolivinelimnpo4andlifepo4usinghybriddensityfunctionaltheory AT cedergerbrand comparisonofsmallpolaronmigrationandphaseseparationinolivinelimnpo4andlifepo4usinghybriddensityfunctionaltheory |