Impact of Solvent Impurities from Upscaled Synthesis and Their Purification in Lithium Metal Batteries

Fluorinated ether electrolytes are promising for high-energy-density lithium metal batteries, yet their translation to larger-scale production requires systematic control of solvent impurities generated during synthesis and purification. Using 2-(2-(2,2-difluoroethoxy)ethoxy)–1,1,1-trifluoroethane (F5DEE) as a high-performance model solvent, we compare gram- and kilogram-scale batches to correlate impurity origin, purification, and electrochemistry. Although upscaled F5DEE shows >99% purity by standard techniques, ppm-level moisture and organic impurities reduce Li Coulombic efficiency and increase cell variability. We classify impurities by generation pathway into retained intermediates, starting-material-derived analogues, side-reaction products, and purification-introduced residues. Distillation, adsorption, and reactive purification implicate water, alkoxide-derived byproducts, and amines as key performance-limiting species. However, excessive purification generates secondary impurities that degrade performance, revealing a removal–generation trade-off. Thermal, electrochemical, operando microcalorimetry, and online mass spectrometry analyses reveal impurity-dependent current-collector corrosion, heat release, gas evolution, and full-cell degradation. This route-resolved, source-to-consequence workflow provides a transferable qualification framework for electrolyte solvent scale-up.