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Issue 3, 2017
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An optimised synthesis of high performance radiation-grafted anion-exchange membranes

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Abstract

High performance benzyltrimethylammonium-type alkaline anion-exchange membranes (AEM), for application in electrochemical devices such as anion-exchange membrane fuel cells (AEMFC), were prepared by the radiation grafting (RG) of vinylbenzyl chloride (VBC) onto 25 μm thick poly(ethylene-co-tetrafluoroethylene) (ETFE) films followed by amination with trimethylamine. Reductions in the electron-beam absorbed dose and amount of expensive, potentially hazardous VBC were achieved by using water as a diluent (reduced to 30–40 kGy absorbed dose and 5 vol% VBC) instead of the prior state-of-the-art method that used organic propan-2-ol diluent (required 70 kGy dose and 20 vol% VBC monomer). Furthermore, the water from the aqueous grafting mixture was easily separated from the residual monomer (after cooling) and was reused for a further grafting reaction: the resulting AEM exhibited an ion-exchange capacity of 2.1 mmol g−1 (cf. 2.1 mmol g−1 for the AEM made using a fresh grafting mixture). The lower irradiation doses resulted in mechanically stronger RG-AEMs compared to the reference RG-AEM synthesised using the prior state-of-the-art method. A further positive off-shoot of the optimisation process was the discovery that using water as a diluent resulted in an enhanced (i.e. more uniform) distribution of VBC grafts as proven by Raman microscopy and corroborated using EDX analysis: this led to enhancement in the Cl anion-conductivities (up to 68 mS cm−1 at 80 °C for the optimised fully hydrated RG-AEMs vs. 48 mS cm−1 for the prior state-of-the-art RG-AEM reference). A down-selected RG-AEM with an ion-exchange capacity = 2.0 mmol g−1, that was synthesised using the new greener protocol with a 30 kGy electron-beam absorbed dose, led to an exceptional beginning-of-life H2/O2 AEMFC peak power density of 1.16 W cm−2 at 60 °C in a benchmark test using industrial standard Pt-based electrocatalysts and unpressurised gas supplies: this was higher than the 0.91 W cm−1 obtained with the reference RG-AEM (IEC = 1.8 mmol g−1) synthesised using the prior state-of-the-art protocol.

Graphical abstract: An optimised synthesis of high performance radiation-grafted anion-exchange membranes

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Publication details

The article was received on 09 Sep 2016, accepted on 23 Nov 2016 and first published on 23 Nov 2016


Article type: Paper
DOI: 10.1039/C6GC02526A
Citation: Green Chem., 2017,19, 831-843
  • Open access: Creative Commons BY license
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    An optimised synthesis of high performance radiation-grafted anion-exchange membranes

    L. Wang, E. Magliocca, E. L. Cunningham, W. E. Mustain, S. D. Poynton, R. Escudero-Cid, M. M. Nasef, J. Ponce-González, R. Bance-Souahli, R. C. T. Slade, D. K. Whelligan and J. R. Varcoe, Green Chem., 2017, 19, 831
    DOI: 10.1039/C6GC02526A

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