Weakly Coordinating Diluent Modulated Solvation Chemistry for High-Performance Sodium Metal Batteries

Diluents have been extensively employed to overcome the disadvantages of high viscosity and sluggish kinetics of high-concentration electrolytes, but generally do not change the pristine solvation structure. Herein, a weakly coordinating diluent, hexafluoroisopropyl methyl ether (HFME), is applied to regulate the coordination of Na+ with diglyme and anion and form a diluent-participated solvate. This unique solvation structure promotes the accelerated decomposition of anions and diluents, with the construction of robust inorganic-rich electrode-electrolyte interphases. In addition, the introduction of HFME reduces the desolvation energy of Na+, improves ionic conductivity, strengthens the antioxidant, and enhances the safety of the electrolyte. As a result, the assembled Na||Na symmetric cell achieves a stable cycle of over 1800 h. The cell of Na||P'2-Na0.67MnO2 delivers a high capacity retention of 87.3 % with a high average Coulombic efficiency of 99.7 % after 350 cycles. This work provides valuable insights into solvation chemistry for advanced electrolyte engineering. A novel diluent-participated solvation electrolyte is designed to afford a new path to advanced electrolyte engineering. By introducing the weak solvation diluent to incorporate into the Na+ solvation structure, the electrolyte exhibits improved ionic conductivity, low desolvation energy, excellent oxidation resistance, high safety, and highly robust and conductive EEI films with superior electrochemical performances.+ image