Synergetic Dual‐Additive Electrolyte Enables Highly Stable Performance in Sodium Metal Batteries

Abstract Sodium (Na)‐metal batteries (SMBs) are considered one of the most promising candidates for the large‐scale energy storage market owing to their high theoretical capacity (1,166 mAh g ⁻¹ ) and the abundance of Na raw material. However, the limited stability of electrolytes still hindered the application of SMBs. Herein, sulfolane (Sul) and vinylene carbonate (VC) are identified as effective dual additives that can largely stabilize propylene carbonate (PC)‐based electrolytes, prevent dendrite growth, and extend the cycle life of SMBs. The cycling stability of the Na/NaNi _0.68 Mn _0.22 Co _0.1 O ₂ (NaNMC) cell with this dual‐additive electrolyte is remarkably enhanced, with a capacity retention of 94% and a Coulombic efficiency (CE) of 99.9% over 600 cycles at a 5 C (750 mA g ⁻¹ ) rate. The superior cycling performance of the cells can be attributed to the homogenous, dense, and thin hybrid solid electrolyte interphase consisting of F‐ and S‐containing species on the surface of both the Na metal anode and the NaNMC cathode by adding dual additives. Such unique interphases can effectively facilitate Na‐ion transport kinetics and avoid electrolyte depletion during repeated cycling at a very high rate of 5 C. This electrolyte design is believed to result in further improvements in the performance of SMBs.