Controlling Solvation and Solid‐Electrolyte Interphase Formation to Enhance Lithium Interfacial Kinetics at Low Temperatures

Abstract Operation of lithium‐based batteries at low temperatures (<0 °C) is challenging due to transport limitations as well as sluggish Li + kinetics at the electrode interface. The complicated relationships among desolvation, charge transfer, and transport through the solid electrolyte interphase (SEI) at low temperatures are not well understood, hindering electrolyte development. Here, an ether/hydrofluoroether and fluoroethylene carbonate (FEC)‐based ternary solvent electrolyte is developed to improve Li cycling at low temperatures (Coulombic efficiency of 93.3% at ‐40 °C), and the influence of the local solvation structure on interfacial Li + kinetics and SEI chemistry is further revealed. The hydrofluoroether cosolvent allows for modulation of the solvation structure, thereby enabling facile Li + desolvation while forming an inorganic‐rich SEI, which are both beneficial for lowering Li + kinetic barriers at the interface. This cosolvent also increases the oxidative stability of the electrolyte to over 4.0 V versus Li/Li + , thereby enabling cycling of NMC‐based full cells at −40 °C. This study advances the understanding of the influence of Li + solvation structure, SEI chemistry, and interfacial Li + kinetics on Li electrochemistry at low temperatures, providing new design considerations for creating effective low‐temperature electrolyte systems.