Na2FeSiO4 as a sodium-ion battery material: A computational perspective

Abstract

Polyanionic silicate-based cathode materials have attracted considerable attention due to their intrinsic structural stability, strong thermal and chemical resistance, and ability to achieve high operating voltages through the inductive effects of polyanion groups. In this study, atomistic simulations were conducted to explore the energetics of intrinsic point defect formation, Na-ion migration pathways, and dopant incorporation in Na2FeSiO4, providing key insights into its viability as a cathode material for sodium-ion batteries (SIBs). Among the native defects, the Na Frenkel pair exhibited the lowest formation energy, suggesting a natural preference for vacancy-mediated Na-ion migration. The calculated migration energy barriers of 0.38 and 0.41 eV further support the material’s capability for efficient sodium-ion transport. Doping analysis identified K, Zn, and Ge as the most favorable isovalent dopants at the Na, Fe, and Si sites, respectively, while Ga showed a strong tendency to substitute at Fe sites and facilitate Na-vacancy formation. Furthermore, Al substitution at the Si site was found to increase the overall sodium content in the lattice. The electronic structure of these promising dopants was further investigated using density functional theory (DFT), offering deeper insights into their influence on the electrochemical behavior of Na2FeSiO4.