Revealing the Mechanism of Sodium Diffusion in NaxFePO4 Using an Improved Force Field

Olivine NaFePO4 is a promising cathode material for Na-ion batteries. Intermediate phases such as Na0.66FePO4 govern phase stability during intercalation-deintercalation processes, yet little is known about Na+ diffusion in NaxFePO4 (0 < x < 1). Here we use an advanced simulation technique, Ra...

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Detalles Bibliográficos
Autores: Rincón, M., Lozano, A., Escribano, B., Carrasco, J., Akhmatskaya, E.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2018
País:España
Institución:Basque Center for Applied Mathematics (BCAM)
Repositorio:BIRD. BCAM's Institutional Repository Data
OAI Identifier:oai:bird.bcamath.org:20.500.11824/779
Acceso en línea:http://hdl.handle.net/20.500.11824/779
Access Level:acceso embargado
Palabra clave:NaFePO4
energy storage
molecular simulation
diffusion
sampling
force field development
density functional theory
Descripción
Sumario:Olivine NaFePO4 is a promising cathode material for Na-ion batteries. Intermediate phases such as Na0.66FePO4 govern phase stability during intercalation-deintercalation processes, yet little is known about Na+ diffusion in NaxFePO4 (0 < x < 1). Here we use an advanced simulation technique, Randomized Shell Mass Generalized Shadow Hybrid Monte Carlo Method (RSM-GSHMC) in combination with a specifically developed force field for describing NaxFePO4 over the whole range of sodium compositions, to thoroughly examine Na+ diffusion in this material. We reveal a novel mechanism through which Na+/Fe2+ antisite defect formation halts transport of Na+ in the main diffusion direction [010], while simultaneously activating diffusion in the [001] channels. A similar mechanism was reported for Li+ in LiFePO4, suggesting that a transition from one- to two-dimensional diffusion prompted by antisite defect formation is common to olivine structures, in general.