Zwitterion-coated graphene-oxide-doped composite membranes for proton exchange membrane applications

•Polybenzimidazole/zwitterion-coated graphene oxide (ZC-GO) membranes were prepared.•The membranes exhibited low swelling ratios and significant proton conductivities.•The potential of the membranes for direct methanol fuel cell applications was shown.

Zwitterion-coated graphene oxide (ZC-GO) containing ammonium and sulfonic acid groups was synthesized, and various amounts were incorporated into polybenzimidazole (PBI). The effect of the ZC-GO content on the properties of PBI/ZC-GO composite membranes for direct methanol fuel cell (DMFC) applications was investigated. The structure of ZC-GO was confirmed using Fourier-transform infrared spectroscopy, and the purity and structure of PBI were investigated using proton nuclear magnetic resonance spectroscopy. With increasing ZC-GO content, the proton conductivity, methanol permeability, water uptake, and swelling ratio of the composites increased, whereas the thermal stability decreased. Notably, the composite membrane containing 25 wt% ZC-GO exhibited a high proton conductivity (4.12×10−2 S cm−1 at 90 °C and RH 100%) and low methanol permeability (1.38×10−7 cm2 s−1 at 25 °C), which is much lower than that of Nafion 117 under the same conditions. The excellent properties of the composite membranes can be attributed to the homogeneous dispersion of ZC-GO and the formation of proton-transport channels in the membranes. This investigation demonstrates the potential of PBI/ZC-GO composite membranes for DMFC applications.