Positron annihilation lifetime study of Nafion/titanium dioxide nano-composite membranes

•PAL is applied to investigate size and number density of free volumes in Nafion/TiO2 membrane.•The proton transporting ability is correlated with the properties of free volume.•PAL is powerful for illuminating the relationship between structure and ion transport.

Positron annihilation lifetime (PAL) technique is applied for investigation of size and number density of free volumes in Nafion/TiO2-nanoparticles composite membrane. The proton transporting ability is correlated with the properties of free volume inside the membrane. It is revealed that composite membrane with 5 wt% of TiO2 nano-fillers exhibits good electrochemical performance under reduced humidity and it can be saturated with water at relative humidity of 50%, under which ionic clusters and proton transporting channels are formed, indicating that composite membranes with 5 wt% of TiO2 nano-fillers are effective electrolyte for fuel cells operated at reduced humidification levels. The results suggest that PAL can be a powerful tool for elucidating the relationship between microstructure and ion transport in polymer electrolyte membranes.