Sodiophilic Substrate Induces NaF‐Rich Solid Electrolyte Interface for Dendrite‐Free Sodium Metal Anode

Abstract 3D substrate with abundant sodiophilic active sites holds promise for implementing dendrite‐free sodium metal anodes and high‐performance sodium batteries. However, the heightened electrode/electrolyte side reactions stemming from high specific surface area still hinder electrode structure stability and cycling reversibility, particularly under high current densities. Herein, the solid electrolyte interface (SEI) component is regulated and detrimental side reactions are restrained through the uniform loading of Na–Sn alloy onto a porous 3D nanofiber framework (NaSn‐PCNF). The strong interaction between Na–Sn alloy and PF₆⁻ anions facilitates the dissociation of sodium salts and releases more free sodium ions for effective charge transfer. Simultaneously, the modulations of the interfacial electrolyte solvation structure and the construction of a high NaF content SEI layer stabilize the electrode/electrolyte interface. NaSn‐PCNF symmetrical battery demonstrates stable cycling for over 600 h with an ultralow overpotential of 24.5 mV under harsh condition of 10 mA cm⁻² and 10 mAh cm⁻². Moreover, the full cells and pouch cells exhibit accelerated reaction kinetics and splendid capacity retention, providing valuable insights into the development of advanced Na substrates for high‐energy sodium metal batteries.