Non-fluorinated pre-irradiation-grafted (peroxidated) LDPE-based\ud anion-exchange membranes with high performance and stability

摘要

Radiation-grafted anion-exchange membrane (RG-AEM) research has predominantly focused on the chemical stability of\udthe polymer-bound positively-charged head-groups that enable anion conduction. The effect of the backbone polymer\udchemistry, of the precursor film, on RG-AEM stability has been studied to a lesser extent and not for RG-AEMs made from\udpre-irradiation grafting of polymer films in air (peroxidation). The mechanical strength of polymer films is generally\udweakened by exposure to high radiation doses (e.g. from a high-energy e–-beam) and this is mediated by chemical\uddegradation of the main chains: fluorinated films mechanically weaken at lower absorbed doses compared to nonfluorinated\udfilms. This study systematically compares the performance difference between RG-AEMs synthesised from a\udnon-fluorinated polymer film (low-density polyethylene – LDPE) and a partially-fluorinated polymer film (poly(ethylene-cotetrafluoroethylene)\ud– ETFE) using the peroxidation method (pre-irradiation in air using an e–-beam). Both the LDPE and\udETFE precursor films used were 25 μm in thickness, which led to RG-AEMs of hydrated thicknesses in the range 52 – 60 μm.\udThe RG-AEMs (designated LDPE-AEM and ETFE-AEM, respectively) all contained identical covalently-bound\udbenzyltrimethylammonium (BTMA) cationic head-groups. An LDPE-AEM achieved a OH– anion conductivity of 145 mS cm-1\udat 80 °C in a 95% relative humidity environment and a chloride Cl– anion conductivity of 76 mS cm-1 at 80 °C when fully\udhydrated. Alkali stability testing showed that the LDPE-AEM mechanically weakened to a much lower extent when treated\udin aqueous alkaline solution compared to the ETFE-AEM. This LDPE-AEM outperformed the ETFE-AEM in H2/O2 anionexchange\udmembrane fuel cell (AEMFC) tests due to high anion conductivity and enhanced in situ water transport (due to the\udlower density of the LDPE precursor): a maximum power density of 1.45 W cm-2 at 80 °C was achieved with an LDPE-AEM\udalongside a Pt-based anode and cathode (cf. 1.21 mW cm-2 for the benchmark ETFE-AEM). The development of more\udmechanically robust RG-AEMs has, for the first time, led to the ability to routinely test them in fuel cells at 80 °C (cf. 60 °C\udwas the prior maximum temperature that could be routinely used with ETFE-based RG-AEMs). This development facilitates\udthe application of non-Pt catalysts: 931 mW cm-2 was obtained with the use of a Ag/C cathode at 80 °C and a Ag loading of\ud0.8 mg cm-2 (only 711 mW cm-2 was obtained at 60 °C). This first report on the synthesis of large batch size LDPE-based RGAEMs,\udusing the commercially amenable peroxidation-type radiation-grafting process, concludes that the resulting LDPEAEMs\udare superior to ETFE-AEMs (for the intended applications).