Electrolyte Design for Lithium Metal Anode‐Based Batteries Toward Extreme Temperature Application

Abstract Lithium anode‐based batteries (LBs) are highly demanded in society owing to the high theoretical capacity and low reduction potential of metallic lithium. They are expected to see increasing deployment in performance critical areas including electric vehicles, grid storage, space, and sea vehicle operations. Unfortunately, competitive performance cannot be achieved when LBs operating under extreme temperature conditions where the lithium‐ion chemistry fail to perform optimally. In this review, a brief overview of the challenges in developing LBs for low temperature (<0 °C) and high temperature (>60 °C) operation are provided followed by electrolyte design strategies involving Li salt modification, solvation structure optimization, additive introduction, and solid‐state electrolyte utilization for LBs are introduced. Specifically, the prospects of using lithium metal batteries (LMBs), lithium sulfur (Li‐S) batteries, and lithium oxygen (Li‐O 2 ) batteries for performance under low and high temperature applications are evaluated. These three chemistries are presented as prototypical examples of how the conventional low temperature charge transfer resistances and high temperature side reactions can be overcome. This review also points out the research direction of extreme temperature electrolyte design toward practical applications.