Further enhancement in the energy densities of rechargeable lithium batteries calls for novel cell chemistry with advanced electrode materials that are compatible with suitable electrolytes without compromising the overall performance and safety, especially when considering high‐voltage applications. Significant advancements in cell chemistry based on traditional organic carbonate‐based electrolytes may be successfully achieved by introducing fluorine into the salt, solvent/cosolvent, or functional additive structure. The combination of the benefits from different constituents enables optimization of the electrolyte and battery chemistry toward specific, targeted applications. This Review aims to highlight key research activities and technical developments of fluorine‐based materials for aprotic non‐aqueous solvent‐based electrolytes and their components along with the related ongoing scientific challenges and limitations. Ionic liquid‐based electrolytes containing fluorine will not be considered in this Review.

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Perspective on recent improvements in experiment and theory towards realizing lithium metal electrodes with liquid electrolytes.