This invention is directed to aqueous redox flow batteries comprising ionically charged redox active materials and separators, wherein the separator is about 100 microns or less and the flow battery is capable of (a) operating with a current efficiency of at least 85% with a current density of at least about 100 mA/cm2; (b) operating with a round trip voltage efficiency of at least 60% with a current density of at least about 100 mA/cm2; and/or (c) giving rise to diffusion rates through the separator for the first active material, the second active material, or both, of about 1×10−7 mol/cm2-sec or less.