Organic–inorganic hybrid proton exchange membranes based on silicon-containing polyacrylate nanoparticles with phosphotungstic acid

A series of silicon-containing polyacrylate nanoparticles (SiPANPs) were successfully synthesized by simple emulsifier-free emulsion polymerization technique. The resulting latex particles were characterized by Fourier transform infrared (FTIR) spectrometry, dynamic light scattering (DLS) analysis, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The SiPANP membranes and SiPANP/phosphotungstic acid (SiPANP/PWA) hybrid membranes were also prepared and characterized to evaluate their potential as proton exchange membranes in proton exchange membrane fuel cell (PEMFC). Compared with the pure SiPANP membrane, the hybrid membranes displayed lower thermal stability. However, the degradation temperatures were still above 190 °C, satisfying the requirement of thermal stability for PEMFC operation. In addition, the hybrid membranes showed lower water uptake but higher proton conductivity than the SiPANP precursor. The proton conductivity of the hybrid membranes was in the range of 10⁻³ to 10⁻² S cm⁻¹ and increased gradually with PWA content and temperature. The excellent hydrolytic stability was also observed in the hybrid membranes because of the existence of crosslinked silica network. The good thermal stability, reasonable water uptake, excellent hydrolytic stability, suitable proton conductivity and cost effectiveness make these hybrids quite attractive as proton exchange membranes for PEMFC applications.     

Composite membranes based on sulfonated poly(aryl ether ketone)s containing the hexafluoroisopropylidene diphenyl moiety and poly(amic acid) for proton exchange membrane fuel cell application

Composite membranes based on sulfonated poly(aryl ether ketone)s containing the hexafluoroisopropylidene diphenyl moiety and poly(amic acid) with oligoaniline in the main chain have been prepared and immersed in H₃PO₄ to obtain acid-doped composite films. As expected, the water uptake values and methanol permeability of the composite membranes decrease with the increase of the weight fraction of PAA in the membrane matrix. Notably, the SPEEK-6F/PAA-15 shows a water uptake of 13.2% and a methanol permeability of 0.9 × 10⁻⁷ cm² s⁻¹, which are much lower than those of the Nafion (28.6% and 15.5 × 10⁻⁷ cm² s⁻¹, respectively). Although the proton conductivities decrease after the addition of PAA, higher selectivity values are obtained with the composite membranes. Therefore, the SPEEK-6F/PAA blend membranes, with the improved proton conductivity, methanol resistance and good thermal stability, can be used as a good alternative for proton conductive membranes with potential application in proton exchange membrane fuel cells (PEMFCs).     

Novel hybrid membranes based on polybenzimidazole and ETS-10 titanosilicate type material for high temperature proton exchange membrane fuel cells: A comprehensive study on dense and porous systems

Novel hybrid membranes based on polybenzimidazole (PBI) and ETS-10 titanosilicate type materials functionalized with sulfonic groups have been developed for high temperature PEMFC applications. In particular, 45% porous ETS-10/PBI electrolyte membranes in porosity have been reported for the first time in this work. A clear conduction outperforming is shown by porous PBI + 3 wt.% SO₃H-ETS-10 doped at 50 °C, attaining “in-plane” conductivity values up to 74 mS cm⁻¹ at 180 °C under dry N₂ flow. The transport selectivity of the as prepared dense and porous PBI based membranes has been evaluated by comparison of “in-plane” conductivity/methanol permeability values at 50 °C, 100 °C and 150 °C. Accounting from that, dense pure PBI membranes are preferred at 50 °C (4.7 × 10⁶ S·s·bar mol⁻¹); whereas at 150 °C, dense PBI + 3% SO₃H-ETS-10 counterparts exhibit the higher conductivity/methanol permeability ratio (2.5 × 10⁸ S·s·bar mol⁻¹).