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Issue 12, 2016
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High performance aliphatic-heterocyclic benzyl-quaternary ammonium radiation-grafted anion-exchange membranes

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Abstract

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-N-methylpiperidinium)- 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-N-methylpyrrolidinium head-group as an improvement to the current de facto benchmark benzyltrimethylammonium head-group.

Graphical abstract: High performance aliphatic-heterocyclic benzyl-quaternary ammonium radiation-grafted anion-exchange membranes

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Publication details

The article was received on 07 Jul 2016, accepted on 03 Oct 2016 and first published on 03 Oct 2016


Article type: Paper
DOI: 10.1039/C6EE01958G
Citation: Energy Environ. Sci., 2016,9, 3724-3735
  • Open access: Creative Commons BY license
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    High performance aliphatic-heterocyclic benzyl-quaternary ammonium radiation-grafted anion-exchange membranes

    J. Ponce-González, D. K. Whelligan, L. Wang, R. Bance-Soualhi, Y. Wang, Y. Peng, H. Peng, D. C. Apperley, H. N. Sarode, T. P. Pandey, A. G. Divekar, S. Seifert, A. M. Herring, L. Zhuang and J. R. Varcoe, Energy Environ. Sci., 2016, 9, 3724
    DOI: 10.1039/C6EE01958G

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