Mechanistic insights into the origin of the oxygen migration barrier
Oxygen ion conductors require high temperatures to exhibit the high ion conductivity needed for practical use. In this work, we related oxygen vacancy formation energy and migration barrier to the electronic structure of perovskites using ab initio simulations. The vacancy formation energy increases...
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | en_US |
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Royal Society of Chemistry
2024
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| Online Access: | https://hdl.handle.net/1721.1/156078 |
| _version_ | 1811083206809616384 |
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| author | Vivona, Daniele Gordiz, Kiarash Meyer, Randall Raman, Sumathy Shao-Horn, Yang |
| author2 | Massachusetts Institute of Technology. Department of Mechanical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Mechanical Engineering Vivona, Daniele Gordiz, Kiarash Meyer, Randall Raman, Sumathy Shao-Horn, Yang |
| author_sort | Vivona, Daniele |
| collection | MIT |
| description | Oxygen ion conductors require high temperatures to exhibit the high ion conductivity needed for practical use. In this work, we related oxygen vacancy formation energy and migration barrier to the electronic structure of perovskites using ab initio simulations. The vacancy formation energy increases with the increasing energy penalty for transferring electrons from oxygen to the highest filled metal states. On the other hand, the migration barrier increases with larger electronic energy penalty for screening the charge that accumulates around the oxygen vacancy. Bringing localized filled electronic states associated with the oxygen vacancy closer to the conduction band or increasing the metal–oxygen band overlap can decrease charge accumulation in the oxygen vacancy and reduce the migration barrier. By investigating the changes in the electronic structure during oxygen migration, the critical role of increasing the charge screening capability of the host lattice local environment in decreasing the migration barrier was further highlighted. Our findings provide new insights into lowering the migration barrier in oxygen ion conductors and trends towards accelerating their discovery. |
| first_indexed | 2024-09-23T12:28:25Z |
| format | Article |
| id | mit-1721.1/156078 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T12:28:25Z |
| publishDate | 2024 |
| publisher | Royal Society of Chemistry |
| record_format | dspace |
| spelling | mit-1721.1/1560782024-09-13T04:38:13Z Mechanistic insights into the origin of the oxygen migration barrier Vivona, Daniele Gordiz, Kiarash Meyer, Randall Raman, Sumathy Shao-Horn, Yang Massachusetts Institute of Technology. Department of Mechanical Engineering Oxygen ion conductors require high temperatures to exhibit the high ion conductivity needed for practical use. In this work, we related oxygen vacancy formation energy and migration barrier to the electronic structure of perovskites using ab initio simulations. The vacancy formation energy increases with the increasing energy penalty for transferring electrons from oxygen to the highest filled metal states. On the other hand, the migration barrier increases with larger electronic energy penalty for screening the charge that accumulates around the oxygen vacancy. Bringing localized filled electronic states associated with the oxygen vacancy closer to the conduction band or increasing the metal–oxygen band overlap can decrease charge accumulation in the oxygen vacancy and reduce the migration barrier. By investigating the changes in the electronic structure during oxygen migration, the critical role of increasing the charge screening capability of the host lattice local environment in decreasing the migration barrier was further highlighted. Our findings provide new insights into lowering the migration barrier in oxygen ion conductors and trends towards accelerating their discovery. 2024-08-13T21:09:20Z 2024-08-13T21:09:20Z 2024-07-25 Article http://purl.org/eprint/type/JournalArticle 2050-7488 https://hdl.handle.net/1721.1/156078 Vivona, Daniele, Gordiz, Kiarash, Meyer, Randall, Raman, Sumathy and Shao-Horn, Yang. 2024. "Mechanistic insights into the origin of the oxygen migration barrier." Journal of Materials Chemistry A. en_US 10.1039/d4ta04049j Journal of Materials Chemistry A Creative Commons Attribution-Noncommercial http://creativecommons.org/licenses/by-nc/4.0/ application/pdf Royal Society of Chemistry Royal Society of Chemistry |
| spellingShingle | Vivona, Daniele Gordiz, Kiarash Meyer, Randall Raman, Sumathy Shao-Horn, Yang Mechanistic insights into the origin of the oxygen migration barrier |
| title | Mechanistic insights into the origin of the oxygen migration barrier |
| title_full | Mechanistic insights into the origin of the oxygen migration barrier |
| title_fullStr | Mechanistic insights into the origin of the oxygen migration barrier |
| title_full_unstemmed | Mechanistic insights into the origin of the oxygen migration barrier |
| title_short | Mechanistic insights into the origin of the oxygen migration barrier |
| title_sort | mechanistic insights into the origin of the oxygen migration barrier |
| url | https://hdl.handle.net/1721.1/156078 |
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