Breaking Aggregation State to Achieve Low‐Temperature Fast Charging of Lithium Metal Batteries

Insufficient ionic conductivity and elevated desolvation energy barrier of electrolytes limit the lithium metal batteries (LMBs) low-temperature applications. Weakly solvating electrolytes (WSEs), with limited lithium salt dissociation capability, are prone to desolvate and drive anion-rich aggregates (AGGs). However, significant AGGs result in increased viscosity and low ionic mobility, contributing to battery failure at low temperatures (≤ -20 oC). Here, we propose and achieve a transformation of solvation structures from AGGs to contact ion pairs (CIPs) through modulating the overall solvation capability, thereby achieving the balance between weak Li+ - solvent interactions and desired ion migration kinetics. Remarkly, CIPs-dominated electrolyte shows a ten-fold increase in ionic conductivity compared to conventional WSEs. The Li||LiFePO4 (LFP) battery achieves more than 1400 cycles with 86.9% capacity retention at 5 C. The practical 1.2 Ah LFP pouch cell delivered 69% of the capacity at 25 oC when cycled at -40 oC. This strategy for solvation structure transformation in WSEs provides a novel approach for the development of electrolytes for low-temperature batteries.