Antifluorite-type Na 5 FeO 4 as a low-cost, environment-friendly cathode with combined cationic/anionic redox activity for sodium ion batteries: a first-principles investigation.

The rapid electrification of our society and the transition towards a larger share of intermittent renewable energy sources in our electricity grids will dramatically increase the demand for cheap energy storage. Sodium ion batteries (SIBs) show a lot of promise to provide the required stationary storage at the grid level at low cost owing to the natural abundance and geographical availability of sodium. In addition, alkali-rich cathode materials exhibiting anionic redox contributions have garnered much attention over the past decade as a strategy to increase the specific capacity. In this work, we investigate for the first time the sodium-rich compound Na 5 FeO 4 as a potential low-cost, environment-friendly cathode for sodium ion batteries from first principles using density functional theory. We investigate three low-energy polymorphs related to the antifluorite structure, verify their dynamical and mechanical stabilities, and show that they exhibit promising ion diffusive properties. As alkali-rich cathode materials are prone to oxygen loss during cycling, we investigate cycling stability with respect to phase transformations and oxygen loss and identify in particular one promising cycling interval that can reversibly shuttle 1.5 Na + per formula unit between Na 5 FeO 4 and Na 3.5 FeO 4 with a gravimetric energy density exceeding 360 W h kg -1 . Investigations into possible redox mechanisms reveal that the charge compensation occurs simultaneously on Fe- and O-atoms in FeO 4 -tetrahedra, which suggests that Na 5 FeO 4 , if realised experimentally as a cathode material, would join the family of combined cationic/anionic redox compounds.