A series of highly proton conductive electrolyte membranes with improved methanol barrier properties are prepared from polyallylamine hydrochloride (PAH) and polystyrene sulfonic acid (PSS) including salt by Layer-by-Layer (LbL) method. The effects of added salt type (NaCl, MgCl2) and salt concentration (1.0 M, 0.1 M) on proton conductivity (σ) and methanol barrier properties of the LbL self-assembled composite membranes are discussed in terms of controlled layer thickness and charge density. Furthermore, the influences of ion type in the multilayered composite membranes are studied in conjunction with physicochemical and thermal properties.
The deposition of the self-assembly of PAH/PSS film on Nafion is followed by UV–Vis spectroscopy and it is observed that the polyelectrolyte layers growth on both sides of Nafion membrane regularly. (PAH/PSS)5–Na+ and (PAH/PSS)5–H+ with 1.0 M NaCl exhibits 49.6 and 27.8% reduction in lower methanol permittivity in comparison with the pristine Nafion®117, respectively, while the proton conductivities are 12.97 and 74.69 mS cm−1. Promisingly, it is found that the membrane selectivity values (Φ) of all multilayered membranes in H+ form are much higher than that of salt form (Na+ and Mg2+) and perfluorosulfonated ionomers reported in the literature. Also, we find out that the use of polyelectrolytes with high charge density causes a further improvement in proton conductivity and methanol barrier properties simultaneously. These encouraging results indicate that upon a suitable choice of LbL deposition conditions, composite membranes exhibiting both high proton conductivity and improved methanol barrier properties can be tailored for fuel cells.