An Ionic Liquid Electrolyte with Enhanced Li+ Transport Ability Enables Stable Li Deposition for High‐Performance Li‐O2 Batteries

Abstract Bis(trifluoromethanesulfonyl)imide‐based ionic liquid (TFSI‐IL) electrolyte could endow Li‐O 2 batteries with low charging overpotential. However, their weak Li + transport ability (LTA) leads to non‐uniform Li deposition. Herein, guided by Sand formula, the LTA of TFSI‐IL electrolyte is greatly enhanced to realize robust Li deposition through introducing hydrofluoroether (HFE) and optimizing electrolyte component ratios to regulate solvation environment. The solvation environment changes from Li(TFSI) 2 − ion pair into ionic aggregate clusters in the optimal electrolyte thanks to the slicing function of HFE toward ionic aggregate network. The transport parameters of Sand formula are synchronously enhanced, resulting in highly robust Li deposition behavior with greatly improved Coulombic efficiency (ca. 97.5 %) and cycling rate (1 mA cm −2 ). Cycling stability of Li‐O 2 batteries was greatly improved (a tiny overpotential rise of 64 mV after 75 cycles).