Despite the high energy density of layered-type cathode materials for Na-ion batteries, their two-dimensional crystal structure suffers a large volume change and phase transition during Na+ de/intercalation, which often results in their poor cycling performances. Thus, a robust three-dimensional framework with minimal structural change is required for stable electrochemical sodium storage. Here, we introduce an earth-abundant element-based trigonal-type Na–Fe–F compound (Na2Fe2F7) with three-dimensionally interconnected FeF6 octahedra and three-dimensional Na+ diffusion pathways. Through combined studies using first-principles calculations and experiments, we confirm that Na2Fe2F7 delivers excellent power-capability due to large three-dimensional Na+ diffusion pathways as well as ultra-long cycling performance due to negligible structural change during Na+ de/intercalation. These results will guide new insights for material discovery for high performance rechargeable batteries.
