(Invited) A Micelle Electrolyte Enabled By Fluorinated Ether Additives for Polysulfide Suppression, High Voltage Cathode, and Li Metal Anode Stabilization

Abstract

The Li-S battery is a promising next-generation technology due to its high theoretical energy density (2600 Wh/kg) and low active material cost. However, poor cycling stability and coulombic efficiency caused by polysulfide dissolution have proven to be major obstacles for a practical Li-S battery implementation. In this work, we develop a novel strategy to suppress polysulfide dissolution using hydrofluoroethers (HFEs) with bi-functional, amphiphlic surfactant-like design: a polar lithiophilic “head” attached to a fluorinated lithiophobic “tail.” A unique solvation mechanism is proposed for these solvents whereby dissociated lithium ions are readily coordinated with lithiophilic “head” to induce self-assembly into micelle-like complex structures. Complex formation is verified experimentally by changing the additive structure and concentration using small angle X-ray and neutron scattering. These HFE-based electrolytes are found to prevent polysulfide dissolution and to have excellent chemical compatibility with lithium metal: Li||Cu stripping/plating tests reveal high coulombic efficiency (>99.5%), modest polarization, and smooth surface morphology of the uniformly deposited lithium. Li-S cells are demonstrated with 1395 mAh/g initial capacity and 71.9% retention over 100 cycles at >99.5% efficiency—evidence that the micelle structure of the amphiphilic additives in HFEs can prohibit polysulfide dissolution while enabling facile Li+ transport and anode passivation. In addition, this type of electrolytes is also stable toward high voltage cathode to enable a lithium metal anode and high voltage cathode high-energy density rechargeable lithium battery.