Anion-exchange membranes (AEM) containing saturated-heterocyclic benzyl-quaternary ammonium (QA) groups synthesised by radiation-grafting onto poly(ethylene-co-tetrafluoroethylene) (ETFE) films are reported. The relative properties of these AEMs are compared with the benchmark radiation-grafted ETFE-g-poly(vinylbenzyltrimethylammonium) AEM. Two AEMs containing heterocyclic-QA head groups were down-selected with higher relative stabilities in aqueous KOH (1 mol dm-3) at 80°C (compared to the benchmark): these 100 μm thick (fully hydrated) ETFE-g-poly(vinylbenzyl-Nmethylpiperidinium)- and ETFE-g-poly(vinylbenzyl-N-methylpyrrolidinium)-based AEMs had as-synthesised ion-exchange capacities (IEC) of 1.64 and 1.66 mmol g-1, respectively, which reduced to 1.36 mmol dm-3 (ca. 17 – 18% loss of IEC) after alkali ageing (the benchmark AEM showed 30% loss of IEC under the same conditions). These down-selected AEMs exhibited as-synthesised Cl- ion conductivities of 49 and 52 mS cm-1, respectively, at 90°C in a 95% relative humidity atmosphere, while the OH- forms exhibited conductivities of 138 and 159 mS cm-1, respectively, at 80°C in a 95% relative humidity atmosphere. The ETFE-g-poly(vinylbenzyl-N-methylpyrrolidinium)-based AEM produced the highest performances when tested as catalyst coated membranes in H2/O2 alkaline polymer electrolyte fuel cells at 60°C with PtRu/C anodes, Pt/C cathodes, and a polysulfone ionomer: the 100 μm thick variant (synthesised from 50 μm thick ETFE) yielded peak power densities of 800 and 630 mW cm-2 (with and without 0.1 MPa back pressurisation, respectively), while a 52 μm thick variant (synthesised from 25 μm thick ETFE) yielded 980 and 800 mW cm-2 under the same conditions. From these results, we make the recommendation that developers of AEMs, especially pendent benzyl-QA types, should consider the benzyl-Nmethylpyrrolidinium head-group as an improvement to the current de facto benchmark benzyltrimethylammonium headgroup

Precise control over polyelectrolyte architecture, engineered for self-assembly of ion-conducting channels, is of fundamental and technological importance to many fields, for example, fuel cells and redox flow batteries and electrodialysis. Building on recent advances with the supramolecular chemistry, we introduce inter/intramolecular cation-dipole interactions between pendent quaternary ammoniums cations and polar polyethylene glycol grafts in an anion-exchange membrane (AEM). Such interactions lead to desirable, ordered ion-conducting pathways when in the membrane form. Comparison of the results of molecular dynamics simulation with 1 H NMR and nano-scale microscopy analyses show that the cation-dipole interactions enhance self-assembly and the formation of interconnected ionic network domains, providing three-dimensional pathways for both water and ion transport. The resultant AEM exhibits high OH − conductivity (49 mS cm −1 at 30 C) and a completive peak power density of 622 mW cm −2 at 70 C when tested in a H 2 /O 2 single-cell alkaline membrane fuel cell.

Radiation-grafted anion-exchange membranes (RG-AEM) are being developed to evaluate a range of chemistries that have relevance to a variety of electrochemical applications including reverse electrodialysis (RED) salinity gradient power. RG-AEMs...

Radiation-grafted anion-exchange ionomer powders were tested in anion-exchange membrane fuel cells.