Quantification of Charge Transport and Mass Deprivation in Solid Electrolyte Interphase for Kinetically‐Stable Low‐Temperature Lithium‐Ion Batteries

Abstract Graphite (Gr)‐based lithium‐ion batteries with admirable electrochemical performance below −20 °C are desired but are hindered by sluggish interfacial charge transport and desolvation process. Li salt dissociation via Li + ‐solvent interaction enables mobile Li + liberation and contributes to bulk ion transport, while is contradictory to fast interfacial desolvation. Designing kinetically‐stable solid electrolyte interphase (SEI) without compromising strong Li + ‐solvent interaction is expected to compatibly improve interfacial charge transport and desolvation kinetics. However, the relationship between physicochemical features and temperature‐dependent kinetics properties of SEI remains vague. Herein, we propose four key thermodynamics parameters of SEI potentially influencing low‐temperature electrochemistry, including electron work function, Li + transfer barrier, surface energy, and desolvation energy. Based on the above parameters, we further define a novel descriptor, separation factor of SEI ( S SEI ), to quantitatively depict charge (Li + /e − ) transport and solvent deprivation processes at Gr/electrolyte interface. A Li 3 PO 4 ‐based, inorganics‐enriched SEI derived by Li difluorophosphate (LiDFP) additive exhibits the highest S SEI (4.89×10 3 ) to enable efficient Li + conduction, e − blocking and rapid desolvation, and as a result, much suppressed Li‐metal precipitation, electrolyte decomposition and Gr sheets exfoliation, thus improving low‐temperature battery performances. Overall, our work originally provides visualized guides to improve low‐temperature reaction kinetics/thermodynamics by constructing desirable SEI chemistry.