Clay–Carbon Nanotubes Hybrid Materials for Nanocomposite Membranes: Advantages of Branched Structure for Proton Transport under Low Humidity Conditions in PEMFCs

A new class of hybrid materials based on carbon nanotubes (CNT) rooted on smectite clays (SWy) was synthesized by catalytic chemical vapor deposition (CCVD) method, and studied to be introduced in a perfluorosulfonic acid (Nafion) membrane. Side-wall chemical oxidation and organo-functionalization of the CNT was performed using organic ester molecules containing hydrophilic groups (−RSO₃H). SWy–CNT nanoadditives were incorporated in the polymer by solution-precipitation method producing highly homogeneous nanocomposite membranes with outstanding mechanical properties. Materials were characterized by a combination of techniques (TGA, Raman, FT-IR, SEM, TEM, and DMA), while a deep investigation on the water transport properties was performed by NMR methods (PFG and relaxation times). Membranes containing SWy–oxCNT–RSO₃H nanoadditives are able to guarantee a very high proton diffusion in “quasi-anhydrous” conditions. Proton mobility is ensured by a correct network created from the long nanotubes (well distributed through the clay nanoplatelets) appropriately functionalized with acid groups. Remarkable are the electrochemical results: the best membrane reaches conductivities of 7 × 10^–2 S cm^–1 at 120 °C and 30% RH, 1 order of magnitude higher than pristine polymer, and a rather high value in the current panorama of the PEMFCs

Ion Dynamics and Mechanical Properties of Sulfonated Polybenzimidazole Membranes for High-Temperature Proton Exchange Membrane Fuel Cells

Polybenzimidazole (PBI)-based membranes are one of the systems of choice for polymer electrolyte fuel cells. Monomer sulphonation is one of the strategies suggested to improve proton transport in these membranes. We report a NMR and dynamic mechanical study aiming to investigate the effect of the sulphonation on the proton dynamics and the mechanical properties of the membranes. The analyses of ¹H self-diffusion coefficients and ¹H and ³¹P spectra versus temperature show that sulphonation causes the formation of interchain cross-links, which involve phosphoric acid molecules and the sulfonic groups. This, in turn, reduces the proton mobility and, consequently, the ionic conductivity. The increase of the membrane stiffness with sulphonation is confirmed by dynamic mechanical analysis through the behavior of the storage modulus