A highly-selective layer-by-layer membrane modified with polyethylenimine and graphene oxide for vanadium redox flow...

A selective composite membrane for vanadium redox flow battery (VRFB) was successfully prepared by layer-by-layer (LbL) technique using a perfluorosulfonic sulfonic acid or Nafion 117 (N117). The composite membrane referred as N117-(PEI/GO)n, was obtained by depositing alternating layers of positively charged polyethylenimine (PEI) and negatively charged graphene oxide (GO) as polyelectrolytes. The physicochemical properties and performance of the pristine and composite membranes were investigated. The membrane showed an enhancement in proton conductivity and simultaneously exhibited a notable 90% reduction in vanadium permeability. This, in turn, results in a well-balanced ratio of proton conductivity to vanadium permeability, leading to high selectivity. The highest selectivity of the LbL membranes was found to be 19.2 × 10⁴ S.min/cm³, which is 13 times higher than the N117 membrane (n = 0). This was translated into an improvement in the battery performance, with the n = 1 membrane showing a 4-6% improvement in coulombic efficiency and a 7-15% improvement in voltage efficiency at current densities ranging from 40 to 80 mA/cm². Furthermore, the membrane displays stable operation over a long-term stability at around 88% at a current density of 40 mA/cm², making it an attractive option for VRFB applications using the LbL technique. The use of PEI/GO bilayers maintains high proton conductivity and VE of the battery, opening up possibilities for further optimization and improvement of VRFBs.