Hybrid functional study of the NASICON-type Na3V2(PO4)3: crystal and electronic structures, and polaron-Na vacancy complex diffusion.

The crystal and electronic structures, electrochemical properties and diffusion mechanism of NASICON-type Na3V2(PO4)3 have been investigated based on the hybrid density functional Heyd-Scuseria-Ernzerhof (HSE06). A polaron-Na vacancy complex model for revealing the diffusion mechanism is proposed for the first time in the field of Na-ion batteries. The bound polaron is found to favorably form at the first nearest V site to the Na vacancy. Consequently, the movement of the Na vacancy will be accompanied by the polaron. Three preferable diffusion pathways are revealed; these are two intra-layer diffusion pathways and one inter-layer pathway. The activation barriers for the intra-layer and inter-layer pathways are 353 meV and 513 meV, respectively. For further comparison, the generalized gradient approximation with an onsite Coulomb Hubbard U (GGA+U) is also employed.