Self-assembled polyelectrolyte multilayer modified Nafion membrane with suppressed vanadium ion crossover for vanadium redox flow batteries

The crossover of vanadium ions through proton-exchange membranes such as those of Nafion is the chief reason that results in the low energy efficiency and high self-discharge rate of vanadium redox flow batteries (VRB). With respect to applicability, the ideal proton-exchange membrane used in VRB should possess simultaneously high proton conductivity and low vanadium ion permeability. Here, we report a novel approach using a polyelectrolyte layer-by-layer self-assembly technique to fabricate a barrier layer onto the surface of Nafion membrane by alternate adsorption of polycation poly(diallyldimethylammonium chloride) (PDDA) and polyanion poly(sodium styrene sulfonate) (PSS), which can suppress the crossover of vanadium ions. The Nafion-[PDDA-PSS]_n membrane (n = the number of multilayers) obtained shows much lower vanadium ion permeability compared with plain Nafion membrane. Accordingly, the VRB with Nafion-[PDDA-PSS]_n membrane exhibits a higher coulombic efficiency (CE) and energy efficiency (EE) together with a slower self-discharge rate than that of Nafion system. The highest CE of 97.6% and EE of 83.9% can be achieved at charge-discharge current density of 80 mA cm^-2 and 20 mA cm^-2, respectively.