Electrochemical cells that cycle lithium ions are provided. The electrochemical cells have an electrode that includes a silicon-containing electroactive material that undergoes volumetric expansion and contraction during the cycling of the electrochemical cell; and an electrolyte system that promotes passive formation of a flexible protective layer comprising a lithium fluoride-polymer composite on one or more exposed surface regions of the silicon-containing electroactive material. The electrolyte system includes a lithium salt, at least one cyclic carbonate, and two or more linear carbonates. At least one of the two or more linear carbonate-containing co-solvents is a fluorinated carbonate-containing co-solvent. The electrolyte system accommodates the volumetric expansion and contraction of the silicon-containing electroactive material to promote long term cycling stability.