(Invited) Operando EPR Study on Radicals in Anion-Exchange Membrane Fuel Cells

In the rapidly developing modern society, there is an urgent need for the wide-ranging availability of advanced and eco-friendly energy sources. One of the possible alternatives is the application of anion exchange membrane fuel cells (AEMFCs) with a catalyst reducing dioxygen efficiently. These promising devices can revolutionize the energy sector since they practically produce no pollution. However, to make them more widely used, several obstacles must be overcome. As a result, vast-ranging investigations focus on improving the properties of conductive polymer membranes [1] and catalysts for the oxygen reduction reaction (ORR) [2]. The durability of the membrane electrode assembly (MEA) is one of the critical requirements for the successful commercialization of anion exchange membrane fuel cells (AEMFCs). Despite significant impacts of nucleophilic degradation on ion-exchange capability and the anionic conductivity of investigated membranes, it is believed to affect only cationic sites of membrane polymers and thus cannot explain the reported loss in the mechanical strength of degraded AEMs. Such a phenomenon might be related to polymer backbone degradation caused by free radicals. This was widely described in the literature in the case of fuel cells using proton-conducting membranes [3] but barely mentioned for AEMFCs [4]. Since the oxidative degradation of hydrocarbon polymers is very well known, we aimed to comprehensively investigate the formation of the short-lived species generated during the operation of AEMFCs as well as stable radicals present in the polymer membranes. We investigated the LDPE-base membranes with Pt black, Pd black, PdAg, and Ag as the ORR catalysts, whereas for HOR the Pt black, Pd black, and NiFe catalysts were used. The in-situ measurements are performed with a micro-AEMFC inserted into a resonator of an electron paramagnetic resonance (EPR) spectrometer, which enables separate monitoring of radicals formed on the anode and cathode sides. The creation of radicals was monitored by the EPR spin trapping technique. In Figure 1 the EPR spectra of DMPO spin adducts trapped during operation of micro-fuel cell placed in EPR spectrometer cavity are presented. In this experiment, the LDPE-base membrane with platinum catalysts on both sides was used. The main detected adducts during the operation of the micro-AEMFC were DMPO-OOH and DMPO-OH on the cathode side and DMPO-H on the anode side. Additionally, we clearly show the formation and presence of stable radicals in AEMs during and after long-term AEMFC operation [5]. Preliminary results suggest that the creation of the short-living radicals during AEMFCs operation is independent of the used membrane. However, the applied catalysts determine the number of detected radicals. The EPR investigations indicate that, in addition to the known chemical degradation mechanisms of the cationic ammonium groups of the membrane, oxidative degradation, including radical reactions, has to be taken into account when the stability of an anion conductive polymer for AEMFCs is investigated. The formation of stable radicals in AEMs was proven for the first time in this study. All short-living radicals formed during the AEMFC operation were fully identified. The presence of radicals in the AEM after AEMFC testing indicates that reactive oxygen species may play a very important role in the degradation mechanism of the anion conducting polymers. Results from this study shed light on the understanding of radical formation and presence in the membranes during AEMFC tests, which in turn may help to solve the challenge of anion exchange membrane stability. Acknowledgments. This work was supported by the Polish National Science Centre (NCN) project OPUS-14, No. 2017/27/B/ST5/01004. References: Dekel, D. R.; Rasin, I. G.; Brandon, S. Predicting Performance Stability of Anion Exchange Membrane Fuel Cells, Power Sources 2019, 420, 118−123. Kostuch A.; Jarczewski S.; Surówka M.K.; Kuśtrowski P.; Sojka Z.; Kruczała K. The joint effect of electrical conductivity and surface oxygen functionalities of carbon supports on the oxygen reduction reaction studied over bare supports and Mn–Co spinel/carbon catalysts in alkaline media, Catal. Technol., 2021, 11, 7578–7591 Łańcucki, L.; Schlick, S.; Danilczuk, M.; Coms, F. D.; Kruczała, K. Sulfonated Poly(Benzoyl Paraphenylene) as a Membrane for PEMFC: Ex Situ and in Situ Experiments of Thermal and Chemical Stability, Polym. Degrad. Stab. 2013, 98 (1), 3. Mustain, W.; Chatenet, M.; Page, M.; Kim, Y. S. Durability Challenges of Anion Exchange Membrane Fuel Cells, Energy Environ. Sci. 2020, 17−19. Wierzbicki, S.; Douglin, J. C.; Kostuch, A.; Dekel D. R.; Kruczała, K. Are Radicals Formed During Anion-Exchange Membrane Fuel Cell Operation?, J. Phys. Chem. Lett., 2020, 11, 7630–7636. Figure 1