First-principles studies on the oxygen vacancy formation in α-Na2FePO4F and β-Na2FePO4F

Abstract

The orthorhombic β-Na2FePO4F has been extensively studied, however, a novel monoclinic α-Na2FePO4F has not been explored sufficiently. Oxygen vacancies (VO) can affect the physical and chemical properties of materials, and oxygen vacancy formation energy reflects the difficulty of VO formation. Using first-principles methods, we have calculated the formation energies of VO and their relevant charge states in both α-Na2FePO4F and β-Na2FePO4F. Our results reveal that charged vacancies (VO+1 or VO+2) are easier to form than neutral vacancies (VO0). The reduction of the Fermi level, the decrease in the oxygen partial pressure, or the increase of the temperature are found to decrease the formation energy of VO. The formation energy of VO in α-Na2FePO4F is slightly lower than that in β-Na2FePO4F. The electronic density of states of α-Na2FePO4F and β-Na2FePO4F suggest that more defect states are introduced into the band gap as the charge states increase. These defect states are mainly the 3d orbitals of the Fe atoms. The introduction of oxygen vacancies distorts the [FeO4F2] octahedra, which affect the charge density distribution and the defect states introduced in the band gap. Significantly, oxygen vacancies have a local impact on the charge density redistribution in both α-Na2FePO4F and β-Na2FePO4F. These findings provide theoretical insights into the formation of oxygen vacancies and the control of oxygen release.