Atomic-Scale Study of NASICON Type Electrode Material: Defects, Dopants and Sodium-Ion Migration in Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>
Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> (NVP), a NASICON-type material, has gained attention as a promising battery cathode owing to its high sodium mobility and excellent structural stability. Using computational simulation techniques...
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2024-12-01
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| author | Vijayabaskar Seshan Poobalasuntharam Iyngaran Poobalasingam Abiman Navaratnarajah Kuganathan |
| author_facet | Vijayabaskar Seshan Poobalasuntharam Iyngaran Poobalasingam Abiman Navaratnarajah Kuganathan |
| author_sort | Vijayabaskar Seshan |
| collection | DOAJ |
| description | Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> (NVP), a NASICON-type material, has gained attention as a promising battery cathode owing to its high sodium mobility and excellent structural stability. Using computational simulation techniques based on classical potentials and density functional theory (DFT), we examine the defect characteristics, diffusion mechanisms, and dopant behavior of the NVP. The study found that the Na Frenkel defect is the most favorable intrinsic defect, supporting the desodiation process necessary for capacity and enabling vacancy-assisted Na-ion migration. The Na migration is anticipated through a long-range zig-zag pathway with an overall activation energy of 0.70 eV. K and Sc preferentially occupy Na and V sites without creating charge-compensating defects. Substituting Mg at the V site can simultaneously increase Na content by forming interstitials and reducing the band gap. Additionally, doping Ti at the V site promotes the formation of Na vacancies necessary for vacancy-assisted migration, leading to a notable improvement in electronic conductivity. |
| format | Article |
| id | doaj-art-8e4554b6868445ecbb205ec0f8fb5e48 |
| institution | DOAJ |
| issn | 2673-7167 |
| language | English |
| publishDate | 2024-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Physchem |
| spelling | doaj-art-8e4554b6868445ecbb205ec0f8fb5e482025-08-20T02:42:25ZengMDPI AGPhyschem2673-71672024-12-0151110.3390/physchem5010001Atomic-Scale Study of NASICON Type Electrode Material: Defects, Dopants and Sodium-Ion Migration in Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>Vijayabaskar Seshan0Poobalasuntharam Iyngaran1Poobalasingam Abiman2Navaratnarajah Kuganathan3Department of Chemistry, University of Jaffna, Jaffna 40000, Sri LankaDepartment of Chemistry, University of Jaffna, Jaffna 40000, Sri LankaDepartment of Chemistry, University of Jaffna, Jaffna 40000, Sri LankaDepartment of Materials, Faculty of Engineering, Imperial College London, London SW7 2AZ, UKNa<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> (NVP), a NASICON-type material, has gained attention as a promising battery cathode owing to its high sodium mobility and excellent structural stability. Using computational simulation techniques based on classical potentials and density functional theory (DFT), we examine the defect characteristics, diffusion mechanisms, and dopant behavior of the NVP. The study found that the Na Frenkel defect is the most favorable intrinsic defect, supporting the desodiation process necessary for capacity and enabling vacancy-assisted Na-ion migration. The Na migration is anticipated through a long-range zig-zag pathway with an overall activation energy of 0.70 eV. K and Sc preferentially occupy Na and V sites without creating charge-compensating defects. Substituting Mg at the V site can simultaneously increase Na content by forming interstitials and reducing the band gap. Additionally, doping Ti at the V site promotes the formation of Na vacancies necessary for vacancy-assisted migration, leading to a notable improvement in electronic conductivity.https://www.mdpi.com/2673-7167/5/1/1Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>defectsdopantsdiffusionDFT |
| spellingShingle | Vijayabaskar Seshan Poobalasuntharam Iyngaran Poobalasingam Abiman Navaratnarajah Kuganathan Atomic-Scale Study of NASICON Type Electrode Material: Defects, Dopants and Sodium-Ion Migration in Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> Physchem Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> defects dopants diffusion DFT |
| title | Atomic-Scale Study of NASICON Type Electrode Material: Defects, Dopants and Sodium-Ion Migration in Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> |
| title_full | Atomic-Scale Study of NASICON Type Electrode Material: Defects, Dopants and Sodium-Ion Migration in Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> |
| title_fullStr | Atomic-Scale Study of NASICON Type Electrode Material: Defects, Dopants and Sodium-Ion Migration in Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> |
| title_full_unstemmed | Atomic-Scale Study of NASICON Type Electrode Material: Defects, Dopants and Sodium-Ion Migration in Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> |
| title_short | Atomic-Scale Study of NASICON Type Electrode Material: Defects, Dopants and Sodium-Ion Migration in Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> |
| title_sort | atomic scale study of nasicon type electrode material defects dopants and sodium ion migration in na sub 3 sub v sub 2 sub po sub 4 sub sub 3 sub |
| topic | Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> defects dopants diffusion DFT |
| url | https://www.mdpi.com/2673-7167/5/1/1 |
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