Preparation and properties of hybrid direct methanol fuel cell membranes by embedding organophosphorylated titania submicrospheres into a chitosan polymer matrix

Organophosphorylated titania submicrospheres (OPTi) are prepared and incorporated into a chitosan (CS) matrix to fabricate hybrid membranes with enhanced methanol resistance and proton conductivity for application in direct methanol fuel cells (DMFC). The pristine monodispersed titania submicrospheres (TiO2) of controllable particle size are synthesized through a modified sol–gel method and then phosphorylated by amino trimethylene phosphonic acid (ATMP) via chemical adsorption, which is confirmed by XPS, FTIR and TGA. The morphology and thermal property of the hybrid membranes are explored by SEM and TGA. The ionic cross-linking between the –PO3H2 groups on OPTi and the –NH2 groups on CS lead to better compatibility between the inorganic fillers and the polymer matrix, as well as a decreased fractional free volume (FFV), which is verified by positron annihilation lifetime spectroscopy (PALS). The effects of particle size and content on the methanol permeability, proton conductivity, swelling and FFV of the membranes are investigated. Compared to pure CS membrane, the hybrid membranes exhibit an increased proton conductivity to an acceptable level of 0.01 S cm−1 for DMFC application and a reduced methanol permeability of 5 × 10−7 cm2 s−1 at a 2 M methanol feed.