High Durability of Pemion^® Proton Exchange Membranes in Cross-Pressure Accelerated Mechanical Stress Tests

Polymer electrolyte membrane fuel cells (PEMFC) are the dominant technology for hydrogen-powered fuel cell electric vehicles in clean transportation systems. To be suitable for commercialization and applicability in real-world use-cases, light and heavy-duty fuel cell vehicles require lifetimes of over 8,000 and 30,000 hours, respectively [1]. Hence, enhancing the durability of all fuel cell components, particularly the proton exchange membrane (PEM), is of great importance. Recently, fuel cell membranes based on hydrocarbon (HC) chemistries have become increasingly common in the literature [2]. Materials with polyaromatic backbones, tunable electrochemical properties, and low reactant permeability are increasingly seen as potential alternatives to incumbent perfluorosulfonic acid (PFSA) materials [2]. Additionally, as restrictions on the use of fluorinated materials in various industries continue to grow, the importance of HC chemistries will as well. Sulfo-phenylated polyphenylenes (sPPPs) are a particular class of HC materials that show promise [3]. However, the phase separation between hydrophilic and hydrophobic domains within sPPPs may not be as discrete as in PFSAs [3], requiring higher ion exchange capacity (IEC) values than PFSAs to achieve similar protonic conductivity. High IEC typically results in greater material hydrophilicity, which can render membranes dimensionally unstable in a fuel cell [4]. State-of-the-art commercial PEMs are now manufactured as thin films (≤ 18 µm), offering small ohmic loss and therefore high fuel cell performance. To improve dimensional stability and eliminate the risks of electrical shorting, PEMs are commonly mechanically reinforced using a porous, inert, and non-ionic substrate, such as expanded polytetrafluoroethylene (ePTFE). In a work by Miyake et al. [5], sulfonated polyphenylene-based ionomer membranes with flexible polyethylene mechanical reinforcement were prepared and the results indicated promising mechanical properties and improved longevity in RH cycling tests. However, there is still a lack of data about the fatigue durability of HC membranes in the literature, and evaluating and comparing the mechanical durability of numerous PEMs with a mechanical reinforcement layer in a traditional wet-dry cycling accelerated stress test would be a time-consuming and thus costly process [6]. In our previous work, [7] we combined constant pressure differential across an ePTFE-reinforced perfluorosulfonic acid (PFSA) ionomer membrane with in-situ RH cycles (ΔP-AMST) to simulate the actual mechanical stresses in the fuel cell environment, while accelerating the durability testing for reinforced PEMs. In this study, ΔP-AMST is used to benchmark the fatigue lifetime curves for Pemion® membranes and compare it with a commercial reinforced PFSA-based PEM. The test temperature was set to 90 °C, and dry and wet (90% RH) phases were 60s and 30s, respectively. The hardware and semi-MEA specifications used for the test are shown in Figure 1a-c. A semitransparent polycarbonate spacer plate with 20 mm thickness and a circular aperture (25.4 mm) in the middle was used to allow free expansion of the membrane (Figure 1d). The cathode side was pressurized to create a cross pressure between the two sides and intensify the stress on the membrane during the RH cycling process. The ultimate failure of the membrane is shown in Figure 1e. The radial stress at the center of the deformed membrane is estimated by Hencky’s solution, as reported in our previous work [7]. Figure 1f demonstrates the estimated nominal stress on the membranes as a function of their lifetimes in terms of RH cycles. According to the fatigue S-N curves, reinforced Pemion® membranes afford longer lifetime than incumbent PFSA materials if the membrane edges are well protected. In addition, the impact of IEC on the fatigue durability of Pemion® membranes is investigated and the results are evaluated against stress of dehydration and dynamic mechanical analysis measurements. Acknowledgements This project was financially supported by Natural Sciences and Engineering Research Council of Canada (NSERC), Ionomr Innovations Inc, Canada Foundation for Innovation (CFI), British Columbia Knowledge Development Fund (BCKDF), Western Economic Diversification Canada (WD), and Canada Research Chairs (CRC). References [1] C.S. Gittleman, H. Jia, E.S. De Castro, C.R. Chisholm, Y.S. Kim, Joule, 5 (2021) 1660-1677. [2] D.W. Shin, M.D. Guiver, Y.M. Lee, Chemical reviews, 117 (2017) 4759-4805. [3] M. Adamski, N. Peressin, S. Holdcroft, Materials Advances, 2 (2021) 4966-5005. [4] S.H. Mirfarsi, A. Karimi, S. Rowshanzamir, M.J. Parnian, Journal of Power Sources, 401 (2018) 73-84. [5] J. Miyake, T. Watanabe, H. Shintani, Y. Sugawara, M. Uchida, K. Miyatake, ACS Materials Au, 1 (2021) 81-88. [6] R. Mukundan, A.M. Baker, A. Kusoglu, P. Beattie, S. Knights, A.Z. Weber, R.L. Borup, Journal of The Electrochemical Society, 165 (2018) F3085. [7] A. Sadeghi Alavijeh, S. Bhattacharya, O. Thomas, C. Chuy, E. Kjeang, Journal of Power Sources Advances, 2 (2020) 100010. Figure 1

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