Interfacial‐Catalysis‐Enabled Layered and Inorganic‐Rich SEI on Hard Carbon Anodes in Ester Electrolytes for Sodium‐Ion Batteries

Abstract Constructing a homogenous and inorganic‐rich solid electrolyte interface (SEI) can efficiently improve the overall sodium‐storage performance of hard carbon (HC) anodes. However, the thick and heterogenous SEI derived from conventional ester electrolytes fails to meet the above requirements. Herein, an innovative interfacial catalysis mechanism is proposed to design a favorable SEI in ester electrolytes by reconstructing the surface functionality of HC, of which abundant CO (carbonyl) bonds are accurately and homogenously implanted. The CO (carbonyl) bonds act as active centers that controllably catalyze the preferential reduction of salts and directionally guide SEI growth to form a homogenous, layered, and inorganic‐rich SEI. Therefore, excessive solvent decomposition is suppressed, and the interfacial Na + transfer and structural stability of SEI on HC anodes are greatly promoted, contributing to a comprehensive enhancement in sodium‐storage performance. The optimal anodes exhibit an outstanding reversible capacity (379.6 mAh g −1 ), an ultrahigh initial Coulombic efficiency (93.2%), a largely improved rate capability, and an extremely stable cycling performance with a capacity decay rate of 0.0018% for 10 000 cycles at 5 A g −1 . This work provides novel insights into smart regulation of interface chemistry to realize high‐performance HC anodes for sodium storage.