W. L. Gore & Associates (Japan)

A PEM fuel cell’s durability and lifetime are affected by various degradation phenomena, among which chemical degradation of PEM material exerts the most damage. Chemical degradation of PEM occurs when reactive radicals such as hydroxyl (·OH) and hydroperoxyl (·OOH) are generated from the decomposition of hydrogen peroxide. The radicals chemically attack the main and side chains of the perfluorosulfonic acid-based PEM and change its internal chemical structure. This leads to excessive membrane thinning and pinhole formation that causes higher gas crossover and electrode shorting inside the PEM fuel cell1. The generation of harmful radicals accelerates in the presence of Fenton’s metal, such as iron (Fe)2. Evaluation of PEM fuel cell chemical degradation durability is performed using long-term pure chemical accelerated stress test (AST) under high temperature (T), low relative humidity (RH), and open circuit voltage (OCV) conditions3. Physical characterization of a membrane sample used in a fuel cell can help to visualize and assess damage incurred during an AST. These results, however, fail to encompass the formation rate of radicals and intermediate degradation products generated during the AST3. To overcome these issues, computational fluid dynamics models are developed that simulate the evolution of degraded products and predict the lifetime of PEM fuel cells4,5.The present work aims to develop an in-situ one-dimensional (1-D) transient chemical degradation model that describes reaction-transport phenomena within the membrane electrode assembly (MEA) in the presence of Fe and Ce cations. This work considers mechanically reinforced GORE-SELECT® 15 µm baseline (MemA) and chemically and mechanically reinforced 12 µm (MemB-Ce) membranes. The developed in-situ model simulates pure chemical AST operating conditions with variable Fe ion loading and follows the computational algorithms originally presented by Wong and Kjeang4. The model successfully predicted that side chain scission is followed by main chain unzipping, as reported in the literature6. The evaluation of the change in ionomer structure by chemical degradation was done by computing the temporal concentration profile of intermediate degraded ionomer species, hydrogen peroxide, and membrane thickness reduction. The 1-D model also encapsulates the concentration profile of Fe2+ and Fe3+ ions across the PEM and predicts their temporal distribution throughout the simulated AST duration under OCV conditions. It was observed that the MemA thickness decreased rapidly in the presence of Fe ions, as shown in Figure 1. The computational parameters and results were calibrated and validated using in-house AST results for MEAs with embedded Fe metallic particles, which were shown to completely dissolve during conditioning and hence treated as uniformly distributed Fe cations with an initial concentration of 900 ppm at the beginning-of-life7. The model identified a limiting Fe ion concentration limit of 100 ppm that accentuates the chemical attack. Experimentally, a low Fe concentration of 10 ppm was determined in the baseline MemA, which also reduced the membrane thickness within 1125 h of operation, as shown in Figure 1. It is known that cerium (Ce) ions can scavenge harmful radicals and increase the lifetime of PEM fuel cells8. The model, therefore, simulates the effectiveness of Ce ions in the MemB-Ce membrane and the temporal distribution of Ce3+/Ce4+ ions and shows a lower rate of membrane thickness reduction, as shown in Figure 1. The modelling framework was, therefore, able to predict PEM fuel cell lifetime in conjunction with the transport behaviour of both harmful and beneficial cations as well as their interactions during the chemical degradation process at OCV conditions. Keywords: PEM fuel cell, fuel cell durability, chemical degradation model, in-situ modelling, iron, cerium Acknowledgements This research was supported by the Natural Sciences and Engineering Research Council of Canada, Canada Foundation for Innovation, British Columbia Knowledge Development Fund, Western Economic Diversification Canada, Ballard Power Systems, and W.L. Gore & Associates. It was also undertaken in part thanks to funding from the Canada Research Chairs program. References J. Healy et al., Fuel Cells, 5, 302–308 (2005).S. Kundu, L. C. Simon, and M. W. Fowler, Polym. Degrad. Stab., 93, 214–224 (2008).Y. Singh, F. P. Orfino, M. Dutta, and E. Kjeang, J. Electrochem. Soc., 164, F1331–F1341 (2017).K. H. Wong and E. Kjeang, J. Electrochem. Soc., 161, F823–F832 (2014).R. B. Ferreira, D. S. Falcão, and A. M. F. R. Pinto, Int. J. Hydrogen Energy, 46, 1106–1120 (2021).L. Ghassemzadeh, K. D. Kreuer, J. Maier, and K. Müller, J. Phys. Chem. C, 114, 14635–14645 (2010).N. Kumar et al., ECS Meet. Abstr., MA2023-02, 1919–1919 (2023).S. M. Stewart, D. Spernjak, R. Borup, A. Datye, and F. Garzon, ECS Electrochem. Lett., 3, F19–F22 (2014). Figure 1

W. L. Gore and Associates, Inc. (Gore) supports the lowest $/kW fuel-cell systems through development of thin, reinforced membranes, ca. 10 µm or less. Thin membranes decrease cost by reducing material content and facilitate higher performance through increased proton conductance and faster water transport. However, it has been postulated that an interfacial water transport resistance, significantly different than the bulk resistance, will dominate for thin membranes. For example, in a previous study, the interfacial effect accounted for half of the total transport resistance for a 10 µm membrane at 30% RH1. Understanding water transport through the membrane is necessary for system-level models to design optimal operation strategies. Gore implemented a protocol and analysis method for characterizing water transport properties of cation exchange membranes. Water flux is driven across the membrane by a chemical-potential gradient at different water activity levels. The water balance is tracked by monitoring the dew point at cell inlet and outlet and closes within 10%. Fick’s law is used to normalize flux data by the activity gradient across cell and inverted to calculate a total transport resistance. Cell hardware with 5 cm2 active area and straight-channel flow field configuration was used. Further details will be discussed in this presentation. Using this method, the bulk permeability of extrusion cast Nafion 11x films is 0.16 µmol/cm/s at 30% relative humidity (RH) and 95 °C, which is in agreement with literature at similar conditions1. An Evaluating the Measurement Process (EMP) study was used to quantify the amount of variation arising from measurement device and operator. With a sample size of 4, the protocol is able to detect a difference in total water transport resistance greater than 0.3 m2-s/mol. The protocol was used to study a series of 700 EW cast film thicknesses from 7 – 70 µm to separate individual contributions to the total water transport resistance, RTotal = RGas + RBulk + RInterfacial. The gas-phase transport resistance, RGas, was separated using hydrogen and nitrogen carrier gasses. The bulk water transport resistance, RBulk, is equal to thickness divided by bulk permeability. Figure 1a shows bulk permeability increases with higher water content, as expected due to the percolating network of water conducting channels2. Typically, any residual resistance is attributed to an interfacial effect, which has been rationalized by the orientation of the hydrophobic backbone toward surface2. In this study, the interfacial resistance is indistinguishable from zero. The equivalent thickness of membrane interface is shown in Figure 1b as a function of RH. ACKNOWLEDGMENTS The authors gratefully acknowledge the contribution of the Electrochemical Products team of W. L. Gore and Associates, Inc. REFERENCES Kienitz, B., Yamada, H., Nonoyama, N. & Weber, A. Z. Interfacial Water Transport Effects in Proton-Exchange Membranes. J. Fuel Cell Sci. Technol. 8, 011013-1-011013-7 (2011).Kusoglu, A. & Weber, A. Z. New Insights into Perfluorinated Sulfonic-Acid Ionomers. Chem. Rev. 117, 987–1104 (2017). Figure 1

[pt] Nos dias atuais, muito mais do que no passado, é sabido que o sucesso de projetos de software depende criticamente de requisitos. Um exemplo de GORE, que significa Engenharia de Requisitos Orientada a Metas, é o Framework i* (iestrela). Este afirma que os requisitos devem representar a intencionalidade do grande número de atores sociais, os quais são pessoas ou sistemas. Dentro desse contexto, existe ainda um vazio de métodos para cobrir o processo da elicitação de metas. Vários métodos para SMA (Sistemas Multi-Agentes) mencionam a elicitação das metas, mas eles não fornecem detalhes de como essa atividade é feita, eles tratam principalmente da modelagem de metas sem antes cuidar dos detalhes da elicitação. Em adição, modelos intencionais como exemplo o Framework i*, podem ser complexos e até mesmo incompreensíveis. Esta tese propõe um método chamado ERi*c – “Engenharia de Requisitos Intencional”, o qual primeiro provê um processo de elicitação que aplica uma abordagem “bottom-up” e simples, com perguntas que podem identificar metas concretas e metas flexíveis. Além disso, o método Eri*c propõe uma solução para reduzir o problema da “escalabilidade” de modelos i* que inclui heurísticas para a especificação desses modelos. O método contém também uma estratégia para fazer diagnósticos de modelos i* de maneira a cobrir o processo de análise de requisitos.

SolIs and pastures were sampled at 96 sites in the Kaiwera district, an area having 12 soil types typical of eastern Southland and South Otago. Analyses indicated that ill-thrift in lambs could be due to low cobalt (Co) Intake. Upland (>300 m a.s.1.) topsoils had lower EDTA extractable Co than lowland topsoils and analysis of soil profile samples indicated that Co had been leached from upper horlzons of upland soils. Upland pastures contained much less Co than lowland pastures and Co concentration was much lower in February than in October. Sheep grazing on upland pasture had very low vitamin B 12 status from October to June and this coincided with low pasture Co concentration Sheep grazing on lowland pasture had adequate vitamin B l2, although pasture Co concentration fell to below 0.06 mg/kg for a short period in summer. We conclude that sheep grazed on upland pastures for long periods need supplementary Co or vitamin B 12 or need to be rotattonally grazed on lowland pasture to build up adequate reserves of vitamin 8, 2 Keywords: ill-thrift. sheep, vitamin B,2, pasture cobalt, seasonal variation