Fluorocarbon surfaclani (potassium nonafluoro-1-bulanesulfonale) is employed Lo prepare the Nafion/fluorocarbon (N/FC) membranes for all vanadium redox flow batteries (VRFB). N/FC membranes with different FC surfactant mass ratios were successfully prepared by a solution casting method. The addition of FC surfactant has effectively suppressed the vanadium ions permeability and improved the proton conductivity of Nation. The N/FC membrane with 5 wt% of FC surfactant (N/FC-5%) exhibits the highest ion selectivity (ratio of proton conductivity to permeability) of 2.0 x 10(6) S min cm(-3), which is 2.1 times higher than that of pure recast Nation (r-Nation) membrane (9.7 x 10(5) S min cm(-3)). Consequently, both coulombic efficiency (CE) and voltage efficiency (VE) of the VRFB with NIFC-5% membrane are higher than that of the VRFB with r-Nafion membrane. The average energy efficiency (product of CE and VE) of the VRFB with N/FC-5% membrane is 11% higher than that of the VRFB with r-Nafion at current density of 40-80 mA cm(-2). (C) 2014 Elsevier B.V. All rights reserved.