Restructuring Electrolyte Solvation by a Versatile Diluent Toward Beyond 99.9% Coulombic Efficiency of Sodium Plating/Stripping at Ultralow Temperatures

Abstract The reversible and durable operation of sodium metal batteries at low temperatures (LT) is essential for cold‐climate applications but is plagued by dendritic Na plating and unstable solid‐electrolyte interphase (SEI). Current Coulombic efficiencies of sodium plating/stripping at LT fall far below 99.9%, representing a significant performance gap yet to be filled. Here, the solvation structure of the conventional 1 m NaPF₆ in diglyme electrolyte by facile cyclic ether (1,3‐dioxolane, DOL) dilution is efficiently reconfigured. DOL diluents help shield the Na⁺‐PF₆⁻ Coulombic interaction and intermolecular forces of diglyme, leading to anomalously high Na⁺‐ion conductivity. Besides, DOL participates in the solvation sheath and weakens the chelation of Na⁺ by diglyme for facilitated desolvation. More importantly, it promotes concentrated electron cloud distribution around PF₆⁻ in the solvates and promotes their preferential decomposition. A desired inorganic‐rich SEI is generated with compositional uniformity, high ionic conductivity, and high Young's modulus. Consequently, a record‐high Coulombic efficiency over 99.9% is achieved at an ultralow temperature of −55 °C, and a 1 Ah capacity pouch cell of initial anode‐free sodium metal battery retains 95% of the first discharge capacity over 100 cycles at −25 °C. This study thus provides new insights for formulating electrolytes toward increased Na reversibility at LT.