Ethylene‐Carbonate‐Free Electrolytes for Rechargeable Li‐Ion Pouch Cells at Sub‐Freezing Temperatures

Abstract Sub‐freezing temperature presents a significant challenge to the survival of current Li‐ion batteries (LIBs) as it leads to low capacity retention and poor cell rechargeability. The electrolyte in commercial LIBs relies too heavily on ethylene carbonate (EC) to produce a stable solid electrolyte interphase (SEI) on graphite (Gr) anodes, but its high melting point (36.4 °C) severely restricts ion transport below 0 °C, causing energy loss and Li plating. Here, a class of EC‐free electrolytes that exhibits remarkable low‐temperature performance without compromising cell lifespan is reported. It is found that at sub‐zero temperatures, EC forms highly resistive SEI that seriously impedes electrode kinetics, whereas EC‐free electrolytes create a highly stable, low‐impedance SEI through anion decomposition, which boosts capacity retention and eliminates Li plating during charging. Pouch‐type LiCoO 2 (LCO)|Gr cells with EC‐free electrolytes sustain 900 cycles at 25 °C with 1 C charge/discharge, and LiNi 0.85 Co 0.10 Al 0.05 O 2 (NCA)|Gr cells last 300 cycles at −15 °C with 0.3 C charge, both among the best‐performing in the literature under comparable conditions. Even at −50 °C, the NCA|Gr cell with EC‐free electrolytes still delivers 76% of its room‐temperature capacity, outperforming EC‐based electrolytes.