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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Bibliographic Details
Main Authors: Vijayabaskar Seshan, Poobalasuntharam Iyngaran, Poobalasingam Abiman, Navaratnarajah Kuganathan
Format: Article
Language:English
Published: MDPI AG 2024-12-01
Series:Physchem
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Online Access:https://www.mdpi.com/2673-7167/5/1/1
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Summary: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.
ISSN:2673-7167