Electrolytes with Solvating Inner Sheath Engineering for Practical Na–S Batteries

Sodium-sulfur (Na-S) batteries with durable Na-metal stability, shuttle-free cyclability, and long lifespan are promising to large-scale energy storages. However, meeting these stringent requirements poses huge challenges with the existing electrolytes. Herein, a localized saturated electrolyte (LSE) is proposed with 2-methyltetrahydrofuran (MeTHF) as an inner sheath solvent, which represents a new category of electrolyte for Na-S system. Unlike the traditional high concentration electrolytes, the LSE is realized with a low salt-to-solvent ratio and low diluent-to-solvent ratio, which pushes the limit of localized high concentration electrolyte (LHCE). The appropriate molecular structure and solvation ability of MeTHF regulate a saturated inner sheath, which features a reinforced coordination of Na+ to anions, enlarged Na+ -solvent distance, and weakened anion-diluent interaction. Such electrolyte configuration is found to be the key to build a sustainable interphase and a quasi-solid-solid sulfur redox process, making a dendrite-inhibited and shuttle-free Na-S battery possible. With this electrolyte, pouch cells with decent cycling performance under rather demanding conditions are demonstrated.