Rechargeable lithium-based battery is hailed as next-generation high-energy-density battery systems. However, growth of lithium dendrites, shuttle effect of lithium polysulfides intermediates and unstable interphase of high-voltage intercalation-type cathodes largely prevent their practical deployment. Herein, to fully conquer the three challenges via one strategy, a novel electrolyte with highly-coordinated solvation structure-in-nonsolvent is designed. On account of the particular electrolyte structure, the shuttle effect is completely suppressed by quasi-solid conversion of S species in Li-S batteries, with a stable cycle performance even at lean electrolyte (5 μL mg−1). Simultaneously, in-situ-formed highly-fluorinated interphases can not only lower Li+ diffusion barrier to ensure uniform nucleation of Li but also improve stability of NCM cathodes, which enable excellent capacity retention of Li‖LiNi0.5Co0.2Mn0.3O2 batteries under conditions toward practical applications (high loading of 2.7 mAh cm−2 and lean electrolyte of 5 mL Ah−1). Besides, the electrolyte is also nonflammable. This electrolyte structure offers useful guidelines for the design of novel organic electrolytes for practical lithium-based batteries.
