Xinming Du,Zhe Wang,Wenchang Liu,Jingmei Xu,Zhaoyu Chen,Chunmei Wang
A series of phenolphthalein-based poly (arylene ether ketone) (PEK) copolymer are synthesized to prepare anion exchange membranes (AEMs). The ion group 1-vinyl imidazole is introduced on the unit of phenolphthalein-based as a hydrophilic segment and cross-linking agent. The structure of resulting membranes was investigated by 1 H NMR and FT-IR. The well-defined microphase-separated structures were verified by TEM and SAXS profiles. The cross-linked membrane of ImPEK-0.4 exhibits high hydroxide conductivity (0.0836 S/cm, at 80 °C), excellent mechanical performance (69.6 MPa) and the maximum swelling ratio is only 7.95% at 80 °C. Furthermore, the excellent alkaline stability is demonstrated by immersing the prepared membrane in 1 M NaOH at 40 °C for 400 h. The ionic conductivity is still high to 0.0381 S/cm for ImPEK-0.4. These results indicate that combining phase separation architecture and crosslinking may possess potential applications for alkaline fuel cells (AFCs).
A series of cross-linked multiblock copoly(arylene ether sulfone) ionomer/nano-ZrO2 (CLQCPAES/nano-ZrO2) composite anion exchange membranes were prepared via block copolymerization, bromomethylation, ultrasonication blending, self-crosslinking, quaternization and alkalization. The structure, and the surface and cross section morphology of the CLQCPAES/nano-ZrO2 composite membranes were characterized by solubility tests, FT-IR, XRD and SEM analyses. The combination of the determined results revealed that the CLQCPAES/nano-ZrO2 composite membranes are a complex cross-linking networks of hydrophobic domains/hydrophilic domains/nano-ZrO2 with a clear zonal distribution of uniform nano-sized particles in the hydrophilic domains, when the nano-filler loading was below 7.5%. Basic performances of the CLQCPAES/nano-ZrO2 composite membranes were assessed to investigate their application in fuel cells in terms of the water uptake, swelling ratio, ion exchange capacity (IEC), hydroxide conductivity, thermal and mechanical properties, and alkaline stability. The modification of anion exchange membranes with multiblock ionomer structures, the use of a cross-linking technique and the introduction of nano-ZrO2 particles greatly enhanced the water uptake, hydroxide conductivity, mechanical properties and alkaline stability of the composite membranes. In particular, the CLQCPAES/7.5%ZrO2 membrane with an IEC value of 1.23 mmol g−1 exhibited the best comprehensive properties and constitutes a good potential candidate for an anion exchange membrane to be used in AEMFCs.
Developing highly ion conductive and desirable electrodialysis (ED) performance anion exchange membranes (AEMs) is of great significance. In this work, we report a strategy for fabricating novel AEMs based on a series of fluoro-methyl poly(arylene ether ketone)s having long-side-chain imidazolium groups for ED. Having hydrophilic conductive flexible side-chain imidazolium groups and rigid hydrophobic backbone within AEM matrix, the optimized AEM (PAEK-60-im) shows low water uptake of 24.9% at 80 °C and desirable ion conductivity of 22.01 mS cm –1 at 30 °C. In NaCl removal application of ED, PAEK-60-im shows the NaCl removal ratio of 69.66% within 120 min, outperforming commercial AEM-Type II (68.98%). Accordingly, it has a higher current efficiency of 83.7% but lower energy consumption of 5.9 kWh kg –1 , compared with the commercial one (82.0%; 6.6 kWh kg –1 ). In particular, in selectrodialysis application, possibly owing to the synergistic effect of pore-size sieving effect resulting from macro-separation morphology and hydration energy difference of SO 4 2– ions (–1000 kJ mol –1 ) and Cl – ions (–317 kJ mol –1 ) in feeding solution, PAEK-60-im shows significantly superior monovalent anion perm-selectivity (Cl − /SO 4 2− ) of 7.70 at 30 min, relative to commercial anion-selective Neosepta ACS (5.27) and many other reported mono-valent anion selective AEMs having elegant surface modified layers. The superior ED performance of the homogeneous PAEK-60-im is suggestive of its potential separation application.
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