Deshielding Anions Enable Solvation Chemistry Control of LiPF₆‐Based Electrolyte toward Low‐Temperature Lithium‐Ion Batteries

Abstract Severe capacity decay under subzero temperatures remains a significant challenge for lithium‐ion batteries (LIBs) due to the sluggish interfacial kinetics. Current efforts to mitigate this deteriorating interfacial behavior rely on high‐solubility lithium salts (e.g., Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), Lithium bis(fluorosulfonyl)imide (LiFSI))‐based electrolytes to construct anion participated solvation structures. However, such electrolytes bring issues of corrosion on the current collector and increased costs. Herein, the most commonly used Lithium hexafluorophosphate (LiPF₆) instead, to establish a peculiar solvation structure with a high ratio of ion pairs and aggregates by introducing a deshielding NO₃⁻ additive for low‐temperature LIBs is utilized. The deshielding anion significantly reduces the energy barrier for interfacial behavior at low temperatures. Benefiting from this, the graphite (Gr) anode retains a high capacity of ≈72.3% at −20 °C, which is far superior to the 32.3% and 19.4% capacity retention of counterpart electrolytes. Moreover, the LiCoO₂/Gr full cell exhibits a stable cycling performance of 100 cycles at −20 °C due to the inhibited lithium plating. This work heralds a new paradigm in LiPF₆‐based electrolyte design for LIBs operating at subzero temperatures.