Guiding Uniform Nucleation and Growth by Engineered Electrolyte‐Philic and Sodiophilic Interface for Dendrite‐Free Sodium Metal Batteries

A sodiophilic interface with poor electrolyte‐philicity often limits fast Na + transport, thereby undermining the benefits of sodiophilicity and triggering uneven plating. Herein, we propose an electrolyte‐philic and sodiophilic interface composed of CH 3 COONa (NaAc) and Na 3 Sb (denoted as SA layer) to synergistically direct uniform Na nucleation and growth. Impressively, the electrolyte‐philicity of the SA layer enables favorable interfacial wetting, while the sodiophilicity further guides Na + ions to contact the interface rapidly and absolutely. This synergy enables more homogeneous Na nucleation and growth, effectively homogenizing Na + flux. Moreover, the increased wettability of the SA layer toward FEC favors NaF formation, which contributes synergistically with its high Young's modulus to suppress dendrite growth. The SA@Na can cycle stably for over 2166 h (0.5 mA cm −2 , 0.5 mAh cm −2 ) at 25°C and 570 h (1.0 mA cm −2 , 0.5 mAh cm −2 ) at 45°C. Moreover, the Na 3 V 2 (PO 4 ) 3 (NVP)||SA@Na cells demonstrate superior rate capacity (66 mAh g −1 at 100 C) and maintain 74 mAh g −1 at 50 C after 2000 cycles (25°C). Even at 45°C, the NVP||SA@Na can maintain stably for 1000 cycles (94.8% capacity retention). Therefore, the rationally designed electrolyte‐philic and sodiophilic interface can effectively regulate Na deposition and suppress dendrite growth.