A novel sulfonated diamine, 4,4′‐bis(4‐amino‐3‐trifluoromethylphenoxy) biphenyl 3,3′‐disulfonic acid (F‐BAPBDS), was successfully synthesized by nucleophilic aromatic substitution of 4,4′‐dihydroxybiphenyl with 2‐chloro‐5‐nitrobenzotrifluoride, followed by reduction and sulfonation. A series of sulfonated polyimides of high molecular weight (SPI‐x, x represents the molar percentage of the sulfonated monomer) were prepared by copolymerization of 1,4,5,8‐naphathlenetetracarboxylic dianhydride (NTDA) with F‐BAPBDS and nonsulfonated diamine. Flexible and tough membranes of high mechanical strength were obtained by solution casting and the electrolyte properties of the polymers were intensively investigated. The copolymer membranes exhibited excellent oxidative stability due to the introducing of the CF3 groups. The SPI membranes displayed desirable proton conductivity (0.52×10−1–0.97×10−1 S·cm−1) and low methanol permeability (less than 2.8×10−7 cm2·s−1). The highest proton conductivity (1.89×10−1 S·cm−1) was obtained for the SPI‐90 membrane at 80°C, with an IEC of 2.12 mequiv/g. This value is higher than that of Nafion 117 (1.7×10−1 S·cm−1). Furthermore, the hydrolytic stability of the obtained SPIs is better than the BDSA and ODADS based SPIs due to the hydrophobic CF3 groups which protect the imide ring from being attacked by water molecules, in spite of its strong electron‐withdrawing behaviors. 相似文献
Summary: SPTES polymers have been successfully synthesized by direct polymerization using tetramethylene sulfone as the solvent. The chemical structures of the SPTES polymers are confirmed by FT‐IR and NMR spectroscopy. The thermal stability is characterized by TGA, and the results show that the sulfonated groups on the polymer backbone are stable up to 300 °C. The measured proton conductivity reaches values above 300 mS · cm−1 at 65 °C and 85% relative humidity. Tough, ductile, free‐standing membranes have been fabricated by solution casting from N,N‐dimethylacetamide, which indicates that the SPTES polymers have excellent membrane‐forming capability and mechanical property. The mono‐functional monomers are introduced into the polymerization to end‐cap the SPTES polymers. The end‐capping groups are effective in improving water resistance, oxidative stability, and retaining the proton conductivity.
Summary: Branched/crosslinked sulfonated polyimide membranes incorporating superior mechanical properties, high proton conductivity, and excellent fuel cell performance were successfully developed. The resulting polymer electrolytes displayed conductivity values of about 0.2 S · cm−1 at 120 °C and 100% relative humidity. In a single H2/O2 fuel cell system at 90 °C, they exhibited reasonably high fuel cell performances comparable to that of Nafion 112.
The structure of the branched/crosslinked sulfonated polyimide membranes studied here. 相似文献
AbstractPoly(vinyl alcohol) (PVA) is a biodegradable, water-soluble membrane that has low methanol permeation and reactive chemical functionalities. Modification of these features makes PVA an attractive proton exchange membrane (PEM) alternative to NafionTM. However, the pristine PVA membrane is a poorer proton conductor than the NafionTM membrane due to the absence of negatively charged ions. Hence, modification of PVA matrixes whilst complying with the requirements of projected applications has been examined extensively. Generally, three modification methods of PVA membranes have been highlighted in previous reports, and these are (1) grafting copolymerization, (2) physical and chemical crosslinking, and (3) blending of polymers. The use of each modification method in different applications is reviewed in this study. Although the three modification methods can improve PVA membranes, the mixed method of modification provides another attractive approach. This review covers recent studies on PVA-based PEM in different fuel cell applications, including (1) proton-exchange membrane fuel cells and (2) direct-methanol fuel cells. The challenges involved in the use of PVA-based PEM are also presented, and several approaches are proposed for further study. 相似文献
