Despite the essential role of ethylene carbonate (EC) in solid electrolyte interphase (SEI) formation, the high Li desolvation barrier and melting point (36 °C) of EC impede lithium-ion battery operation at low temperatures and induce sluggish Li reaction kinetics. Here, we demonstrate an EC-free high salt concentration electrolyte (HSCE) composed of lithium bis(fluorosulfonyl)imide salt and tetrahydrofuran solvent with enhanced subzero temperature operation originating from unusually rapid low-temperature Li transport. Experimental and theoretical characterizations reveal the dominance of intra-aggregate ion transport in the HSCE that enables efficient low-temperature transport by increasing the exchange rate of solvating counterions relative to that of solvent molecules. This electrolyte also produces a <5 nm thick anion-derived LiF-rich SEI layer with excellent graphite electrode compatibility and electrochemical performance at subzero temperature in half-cells. Full cells based on LiNiCoMnO||graphite with tailored HSCE electrolytes outperform state-of-the-art cells comprising conventional EC electrolytes during charge-discharge operation at an extreme temperature of -40 °C. These results demonstrate the opportunities for creating intrinsically robust low-temperature Li technology.
