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

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. © 2024 Wiley-VCH GmbH.