Inorganic‐Enriched Solid Electrolyte Interphases: A Key to Enhance Sodium‐Ion Battery Cycle Stability?

The characteristics of solid electrolyte interphase (SEI) at both the cathode and anode interfaces are crucial for the performance of sodium‐ion batteries (SIBs). The research demonstrates the merits of a balanced organic component, specifically the organic sodium alkyl sulfonate (ROSO 2 Na) featured in this work, in conjunction with the inorganic sodium fluoride (NaF), to enhance the interfacial stability. Using a customized electrolyte, it has optimized the interphase, curbing excess NaF production, and created a thin and uniform NaF/ROSO 2 Na‐rich SEI layer. It offers exceptional protection against interface deterioration, transition metal dissolution, and concurrently ensures a consistent reduction in interfacial impedance. This creative approach results in a substantial improvement in the performance of both the Na 0.9 Ni 0.4 Fe 0.2 Mn 0.4 O 2 cathode and the hard carbon anode. The cathode demonstrates remarkable average Coulombic efficiency exceeding 99.9% and a capacity retention of 81% after 500 cycles. Furthermore, the Ah‐level pouch cell has shown outstanding performance with an 87% capacity retention after 400 cycles. Moving beyond the prevailing focus on inorganic‐rich SEI, these results highlight the effectiveness of the customized organic‐inorganic hybrid SEI formulation in improving SIB technology, offering an adaptable solution that ensures superior interfacial stability.