The regulation of water content in polymeric membranes is important in a number of applications, such as reverse electrodialysis and proton-exchange fuel-cell membranes. External thermal and water management systems add both mass and size to systems, and so intrinsic mechanisms of retaining water and maintaining ionic transport in such membranes are particularly important for applications where small system size is important. For example, in proton-exchange membrane fuel cells, where water retention in the membrane is crucial for efficient transport of hydrated ions, by operating the cells at higher temperatures without external humidification, the membrane is self-humidified with water generated by electrochemical reactions. Here we report an alternative solution that does not rely on external regulation of water supply or high temperatures. Water content in hydrocarbon polymer membranes is regulated through nanometre-scale cracks ('nanocracks') in a hydrophobic surface coating. These cracks work as nanoscale valves to retard water desorption and to maintain ion conductivity in the membrane on dehumidification. Hydrocarbon fuel-cell membranes with surface nanocrack coatings operated at intermediate temperatures show improved electrochemical performance, and coated reverse-electrodialysis membranes show enhanced ionic selectivity with low bulk resistance.

New monomers containing two or four pendent phenyl groups were synthesized by bromination of bis(4-fluorophenyl) sulfone, followed by Suzuki coupling with benzeneboronic acid. The resulting monomers were converted to the corresponding sulfonated monomers having two or four pendent sulfonic acid groups, predominately at the p-phenyl position. Aromatic nucleophilic substitution (SNAr) polycondensation using the di- and tetrasulfonated monomers provided sulfonated poly(arylene ether sulfone) copolymers S2-PAES-xx and S4-PAES-xx, respectively, where xx refers to the molar ratio of the sulfonated to non-sulfonated pendent phenyl monomer. Copoly(arylene ether sulfone)s based on the corresponding non-sulfonated monomers were also synthesized for a parallel study on postpolymerization sulfonation of these copolymers. Postsulfonation occurred predominately at the para-pendent phenyl site, and the reactions were complete within a short time (about 30 min), without evidence of chain degradation. Flexible and tough membranes having high mechanical strength were obtained by solution casting of all four series of copolymers. The copolymers with two or four pendent sulfonic acid groups had high proton conductivities in the range of 44−142 mS/cm for S2-PAES-xx and 51−158 mS/cm for S4-PAES-xx at room temperature, respectively. The methanol permeabilities of these copolymers were in the range of 0.8 × 10−8−15.0 × 10−7 cm2/s, which is lower than Nafion (16.7 × 10−7 cm2/s). The S4-PAES-xx membranes displayed better properties (lower water uptake and higher proton conductivities) than the S2-PAES-xx membranes, which can be attributed to the more blocky architecture of the sulfonic acid groups in the S4 membranes. A combination of high proton conductivities, low water uptake, and low methanol permeabilities for some of the obtained copolymers indicated that they are good candidate materials for proton exchange membrane in fuel cell applications.

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Two series of random sulfonated poly-(benzothiazole-co-benzimidazole) polymers (sPBT-BI) with 70% and 60% degree of sulfonation were evaluated as proton exchange membranes. sPBT was also prepared for a comparative study. The mechanical properties of sPBT-BI were greatly enhanced by incorporation of benzimidazole (BI); sPBT-BI70-10 showed a tensile strength of 125 MPa and elongation at break of 38.9%, an increase of 56.5% and 145%, respectively, compared with sPBT. The solubility, dimensional stability, thermal properties, and oxidative stability of sPBT-BI were also improved. The ionic clusters of sPBT-BI membranes in both AFM phase images and TEM images became narrower with increasing amounts of BI while containing the same molar amount of sulfonic acid groups. This resulted in lower dimensional swelling and higher mechanical strength, but the proton conductivity decreased. However, high proton conductivity was achieved by incorporating an appropriate content of BI. PEMFC H 2 /air single cell performances and durabilities were improved by incorporation of 5% of BI units in sPBT.

Segmented copoly(arylene ether sulfone) membranes having densely sulfonated pendent phenyl blocks were synthesized by the coupling reaction of phenoxide-terminated oligomers with bis(4-hydroxyphenyl) sulfone and decafluorobiphenyl (DFBP), followed by postpolymerization sulfonation of the blocks containing pendent phenyl substituents. The coupling reaction was conducted at relatively low temperature by utilizing highly reactive DFBP to prevent any possible trans-etherification that would randomize the hydrophilic–hydrophobic sequences. Segmented copolymer molecular weights were reasonably high, as determined by viscosity measurements. Postsulfonation occurred selectively on the pendent phenyl substituent to yield hydrophilic blocks that were highly sulfonated in regular sequence on the linked phenyl rings. The resulting polymers gave transparent, flexible, and tough membranes by solution casting. Morphological observation by transmission electron microscopy (TEM) and atomic force microscopy (AFM) showed that the high local concentration and regular sequence of pendent sulfonic acid groups within the hydrophilic blocks enhanced nanophase separation between the hydrophobic and hydrophilic blocks. A comparison of copolymers with similar ion exchange capacities (IECs) indicated that proton conductivity and water uptake were strongly influenced by the hydrophilic block sequence lengths. Proton conductivity and water uptake increased with increasing block length, even at low relative humidity (RH). The ionomer membrane with X20Y20 (X and Y refer to the number of hydrophilic and hydrophobic repeat units, respectively) and 1.82 mequiv/g of IEC had a proton conductivity of 3.6 × 10–2 S/cm at 80 °C and 50% RH, which is comparable to that of perfluorinated ionomer (Nafion) membrane (4.0 × 10–2 S/cm).

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