Anion exchange membrane (AEM) stability is a long-standing challenge that has limited the widespread development and adoption of AEM fuel... Show moreAnion exchange membrane (AEM) stability is a long-standing challenge that has limited the widespread development and adoption of AEM fuel cells. It is essential to understand the mechanism of AEM degradation during fuel cell operation. There are multiple modes of AEM degradation, broadly classified as chemical, mechanical and thermal degradation. Chemical degradation is among the most destructive modes, and can be further sub-divided into nucleophilic degradation (induced by the hydroxide ion), and oxidative degradation (induced by reactive oxygen species). While the former has been extensively studied, there is minimal work on oxidative AEM degradation. The reactive oxygen chemical species produced during the operation of an AEM fuel cell have hitherto not been detected during operation. Given the high pH, it is postulated that superoxide anion radicals (𝑂2∙−), as opposed to hydroxyl radicals, are primarily involved in the degradation progress. The objective of this study was to confirm the 𝑂2∙− formation during AEM fuel cell operation and to monitor in real-time the rate of 𝑂2∙− generation in an operating fuel cell using in-situ fluorescence spectroscopy. 1,3-diphenlisobenzofuran (DPBF) was chosen as the fluorescence probe, the sensitivity of which towards 𝑂2∙− was evaluated by performing ex-situ experiments in a semi-batch reactor. We demonstrate that the fluorescence intensity of this dye selectively decreased upon exposing 𝑂2∙−. DPBF was then incorporated into an AEM (membrane was solution cast after mixing the dye with the casting solution), which was assembled into a fuel cell. 𝑂2∙− generation in an operating AEM fuel cell was then monitored via in-situ fluorescence spectroscopy using a bifurcated optical probe, when the cell was operated in H2/O2 mode. To confirm the impact of 𝑂2∙− on AEM degradation, independent experiments (without dye) were performed under identical conditions, under both H2/O2 and N2/N2 modes, and the ionic conductivity and ion exchange capacity were monitored to estimate degradation extent. From our in-situ fluorescence studies, we were able to estimate the rate constants and activation energy for oxidative AEM degradation in an operating AEM fuel cell. M.S. in Chemical Engineering, July 2016 Show less
