Non-aqueous electrolyte solutions capable of protecting negative electrode materials such as lithium metal and carbonaceous materials in energy storage electrochemical cells (e.g., lithium metal batteries, lithium ion batteries and supercapacitors) include an electrolyte salt, a non-aqueous electrolyte solvent mixture, an unsaturated organic compound 4-methylene-1,3-dioxolan-2-one or 4,5-dimethylene-1,3-dioxolan-2-one, and other optional additives. The 1,3-dioxolan-2-ones help to form a good solid electrolyte interface on the negative electrode surface.