(Invited) Pioneering Solutions to Overcome Trade-off between Conductivity and Hydrogen Permeability in PEM Water Electrolysis with Novel Perfluorinated Sulfonic Acid Polymers

Membraneless Electrolyzers for Low-Cost Hydrogen Production in a Renewable Energy Future

Water electrolyzers and fuel cells can be used to create a closed loop system for space exploration. Electrolyzers allow for reliable self-sustainable generation of hydrogen and oxygen for energy storage, followed by conversion into electrical energy in a fuel cell. A first-order safety concern for water electrolyzer operation is hydrogen crossover. Transport of hydrogen to the oxygen rich anode in proton exchange membrane (PEM) water electrolyzers poses safety concerns when the hydrogen concentration in the anode flow field approaches the hydrogen lower flammability limit (LFL). Hydrogen storage efficiency relies on high hydrogen pressure, leading to pressure-driven hydrogen crossover. Mitigation of hydrogen crossover through research and development of a platinum metal recombination layer has been demonstrated in high performing, durable PEMWEs.1-4 Ouimet4 explored the use of a novel dual recombination layer configuration to mitigate PEM water electrolyzer hydrogen crossover. In addition, the current state of the art for PEM fuel cells and water electrolyzers rely on perfluoro-sulfonated acid (PSFA) based membranes. There are significant challenges facing the use of PSFA-based membranes; namely, environmental contamination and performance limitations. The use of a hydrocarbon membrane allows for the development of a PSFA-free system that shows higher efficiency and durability. Investigation of hydrocarbon membranes pave way for developing a PEM water electrolyzer that will demonstrate improved gas permeability resistance, mechanical strength, and thermal stability.5-8 There is a need for both hydrogen crossover mitigation strategies and durability testing with hydrocarbon membranes.The research outlined in this work is focused on the development of PSFA-free PEM water electrolyzers with low hydrogen crossover. In this work, the dual recombination layer configuration will be incorporated into a hydrocarbon membrane for PEM water electrolysis. Polarization, electrochemical impedance spectroscopy, electrochemical equivalent circuits, distribution of relaxation times, and materials characterization will be used to investigate the cell performance and durability. References G. Mirshekari, R. Ouimet, Z. Zeng, H. Yu, S. Bliznakov, L. Bonville, A. Niedzwiecki, C. Capuano, K. Ayers, and R. Maric, “High-performance and cost-effective membrane electrode assemblies for advanced proton exchange membrane water electrolyzers: Long-term durability assessment,” international journal of hydrogen energy, vol. 46, no. 2, pp. 1526–1539, 2021.Z. Zeng, R. Ouimet, L. Bonville, A. Niedzwiecki, C. Capuano, K. Ayers, A. P. Soleymani, J. Jankovic, H. Yu, G. Mirshekari, et al., “Degradation mechanisms in advanced meas for pem water electrolyzers fabricated by reactive spray deposition technology,” Journal of The Electrochemical Society, vol. 169, no. 5, p. 054536, 2022.A. Martin, D. Abbas, P. Trinke, T. Böhm, M. Bierling, B. Bensmann, S. Thiele, and R. Hanke-Rauschenbach, “Communication—proving the importance of ptinterlayer position in pemwe membranes for the effective reduction of the anodic hydrogen content,” Journal of The Electrochemical Society, vol. 168, no. 9, p. 094509, 2021.R. J. Ouimet, “Catalyst development by a novel fabrication process for energy applications,” University of Connecticut Doctoral Dissertation, 2021.P. Trinke, P. Haug, J. Brauns, B. Bensmann, R. Hanke-Rauschenbach, and T. Turek, “Hydrogen crossover in pem and alkaline water electrolysis: mechanisms, direct comparison and mitigation strategies,” Journal of The Electrochemical Society, vol. 165, no. 7, p. F502, 2018.P. Trinke, B. Bensmann, and R. Hanke-Rauschenbach, “Current density effect on hydrogen permeation in pem water electrolyzers,” International Journal of Hydrogen Energy, vol. 42, no. 21, pp. 14355–14366, 2017.H. Q. Nguyen and B. Shabani, “Proton exchange membrane fuel cells heat recovery opportunities for combined heating/cooling and power applications,” Energy Conversion and Management, vol. 204, p. 112328, 2020.C. Klose, T. Saatkamp, A. Münchinger, L. Bohn, G. Titvinidze, M. Breitwieser, K. D. Kreuer, and S. Vierrath, “All-hydrocarbon mea for pem water electrolysis combining low hydrogen crossover and high efficiency,” Advanced Energy Materials, vol. 10, no. 14, p. 1903995, 2020.

Perfluorinated sulfonic acid (PFSA) polymers are the state-of-the-art material for the proton exchange membrane (PEM) in various electrochemical energy conversion devices, e.g., PEM fuel cells, PEM water electrolyzers, or redox flow batteries, combining chemical and mechanical durability with high proton conductivity.The most prominent example of a PFSA material is NafionTM, which is a so-called long side chain (LSC) ionomer due to its comparably long side chain between the polymer backbone and the charged sulfonyl end group. On the other hand, short side chain (SSC) ionomers like Aquivion® and 3M Ionomer or composite membranes are promising approaches to improve performance in harsh conditions, such as low humidity or high operating temperatures.1 SSC PEMs feature increased water uptake, proton conductivity,2 and crystallinity3 compared to LSC PEMs. Composite PEMs can be specifically tailored to the required operating conditions by carefully designing the interlayers or additives. As the performance and longevity of electrochemical cells are a delicate convolution of various (composite) membrane properties and parameters, a method for evaluating ionomer membrane properties is crucial for rationally engineering optimized PEMs.Here, we use confocal Raman microscopy (CRM) to investigate application-relevant properties of PFSA PEMs and for high-resolution imaging of composite membranes.4 Thus, the high spatial resolution of confocal optical microscopy and the chemical sensitivity of Raman scattering are combined in a single measurement approach. NafionTM, 3M Ionomer, and Aquivion® at varying equivalent weights (EW) feature distinctive Raman spectra (Fig. 1) that show characteristic spectral changes depending on the ionomer’s side chain structure and EW. We show that the EW of these PFSA types can be reliably measured using Raman spectroscopy. Further, parameters such as swelling, ionizable group content, and water uptake can be quantified by CRM non-destructively and contact-free. The diffraction-limited resolution of CRM of less than 2 µm enables a view of the local distribution of these properties and, therefore, allows to image and analyze composite membranes. In summary, we comprehensively study ionomer properties of (composite) membranes and establish CRM as a powerful platform for characterizing advanced PEMs for electrochemical energy deviceReferences A. S. Aricò, A. Di Blasi, G. Brunaccini, F. Sergi, G. Dispenza, L. Andaloro, M. Ferraro, V. Antonucci, P. Asher, S. Buche, D. Fongalland, G. A. Hards, J. D. B. Sharman, A. Bayer, G. Heinz, N. Zandonà, R. Zuber, M. Gebert, M. Corasaniti, A. Ghielmi and D. J. Jones, Fuel Cells, 10(6), 1013–1023 (2010).Y.-C. Park, K. Kakinuma, H. Uchida, M. Watanabe and M. Uchida, Journal of Power Sources, 275, 384–391 (2015).K. D. Kreuer, M. Schuster, B. Obliers, O. Diat, U. Traub, A. Fuchs, U. Klock, S. J. Paddison and J. Maier, Journal of Power Sources, 178(2), 499–509 (2008).M. Maier, D. Abbas, M. Komma, M. S. Mu'min, S. Thiele and T. Böhm, Journal of Membrane Science, 669, 121244 (2023). Figure 1

Hydrogen is widely viewed as a key emerging clean energy carrier for long-term storage and usage in hard-to-abate sectors with high power requirements. However, it is presently produced mainly from fossil fuels, diminishing the potential benefits of reduced emissions. Proton exchange membrane (PEM) water electrolyzers are a critical technology that uses electricity, preferable with low carbon intensity, to split water molecules, producing high purity hydrogen at a high capacity and pressure (>30 atm) while operating under compact, low-temperature conditions. One drawback of state-of-the-art PEM water electrolyzers is the requirement for highly purified, deionized water for robust and efficient operation. The most abundant source of water on the planet is seawater, which has high salt content and other impurities. Typically, seawater is deionized and purified in a separate process, such as reverse osmosis, before being used for electrolysis, driving up the energy requirement and operational cost. This is a viable option for applications where water purification systems are accessible and affordable, and weight requirements are not a factor. Yet, some remote, lightweight applications, such as unmanned aerial vehicles (UAVs), would benefit from a compact system that can directly convert seawater to hydrogen without additional bulky deionization systems. This work presents a compact system that couples the state-of-the-art PEM water electrolyzer with seawater deionization through pervaporation membrane (PVM) deionization. The perfluorinated sulfonic acid (PFSA) electrolyte membrane typically used for PEM water electrolysis was repurposed as an ion-exchange membrane for PVM deionization. The fabrication, testing, and optimization of a lab-scale system that directly utilizes heat from the PEM electrolyzer for the integrated PVM to deionize seawater, which is subsequently used for water electrolysis, will be presented. Funding for this work was provided by the Office of Naval Research under contract N000142412422.

Proton exchange membrane (PEM) water electrolyzers and fuel cells are pivotal for renewable hydrogen technologies. The membrane electrode assembly (MEA) is a critical component in both technologies, with the PEM's core functionality-proton conduction coupled with gas impermeability-dictating overall cell performance and durability. One of the key challenges faced by the commercial perfluorosulfonic acid (PFSA)-based PEMs is the high rate of hydrogen permeation, reducing efficiency and raising safety concerns due to hydrogen-oxygen mixing risks. Therefore, there is an urgent need to mitigate hydrogen crossover in PEMs to enhance operational efficiency and ensure cell safety, particularly for the high-pressure electrolyzers. This review commences by elucidating the hydrogen transport mechanisms in PFSA-based PEMs, along with the methodologies employed to measure hydrogen permeation. Subsequently, the recently developed strategies aimed at reducing hydrogen permeation in PEMs are summarized, with a primary focus on PFSA-based membranes, alongside considering advancements in alternative hydrocarbon polymer membranes. Finally, the challenges that remain are discussed, and potential solutions for addressing hydrogen permeation issues in PEM applications are proposed. This review seeks to provide valuable insights for both academic research and industrial applications, in the pursuit of low-hydrogen permeation PEMs specifically designed for water electrolysis and fuel cell technologies.

Hydrogen, as a clean energy carrier, is of great potential to be an alternative fuel in the future. Proton exchange membrane (PEM) water electrolysis is hailed as the most desired technology for high purity hydrogen production and self-consistent with volatility of renewable energies, has ignited much attention in the past decades based on the high current density, greater energy efficiency, small mass-volume characteristic, easy handling and maintenance. To date, substantial efforts have been devoted to the development of advanced electrocatalysts to improve electrolytic efficiency and reduce the cost of PEM electrolyser. In this review, we firstly compare the alkaline water electrolysis (AWE), solid oxide electrolysis (SOE), and PEM water electrolysis and highlight the advantages of PEM water electrolysis. Furthermore, we summarize the recent progress in PEM water electrolysis including hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) electrocatalysts in the acidic electrolyte. We also introduce other PEM cell components (including membrane electrode assembly, current collector, and bipolar plate). Finally, the current challenges and an outlook for the future development of PEM water electrolysis technology for application in future hydrogen production are provided.

The high cost of noble metals is one of the key factors hindering the large‐scale application of proton exchange membrane (PEM) water electrolyzer for hydrogen production. Recently, single‐atom catalysts (SACs) with a potential of maximum atom utilization efficiency enable lowering the metal amount as much as possible; unfortunately, their durability remains a challenge under PEM water electrolyzer working conditions. Herein, a highly‐stable alloyed Pt SAC is demonstrated through a plasma‐assisted alloying strategy and applies to a PEM water electrolyzer. In this catalyst, single Pt atoms are firmly anchored onto a Ru support via a robust metal–metal bonding strength, as evidenced by these complementary characterizations. This SAC is used in a PEM water electrolyzer system to achieve a cell voltage as low as 1.8 V at 1000 mA cm−2. Impressively, it can operate over 1000 h without obvious decay, and the catalyst is present in the form of individual Pt atoms. To the knowledge, this will be the first SAC attempt at a cell level toward long‐term PEM. This work paves the way for designing durable SACs employed in the actual working condition in the PEM water electrolyzer.

Commercialization of proton exchange membrane (PEM) electrolyzers for green hydrogen production have been recently achieved, but with a limited scale of low gigawatts (GW).1 Large-scale and sustainable deployment of PEM electrolyzers will face the challenges of scarcity and high cost of iridium (Ir) used in the anode to catalyze oxygen evolution reaction (OER). A 1 MW PEM electrolyzer stack currently uses ~0.4 kg of Ir based on an Ir loading of 1.5 mg/cm2, which contributes ~$60k cost per stack.2 Moreover, the Ir production has been about 8 tons/year in recent years.3 This can only support an annual production of 5 GW PEM electrolyzer if assuming 25% Ir is available for PEM electrolyzers with the same Ir loading. Therefore, lowering the Ir loading in PEM electrolyzers is urgently needed to meet the rapid expansion of the PEM electrolysis market.Several groups including Plug have developed supported Ir catalysts to lower the Ir loading by a factor of 5 without sacrifice in efficiency.4-8 However, all support used by far is non- or poorly electrically conductive. The conductivity of the electrodes relies solely on the surface IrOx, which sets stringent limits on the catalyst/electrode development, especially with low Ir contents. Here we first argue from fundamental aspects that the catalysts/electrodes with Ir on conductive support can be free of these limits. We further show that platinum (Pt) and titanium diboride (TiB2) powders are feasible candidates as conductive support for Ir-based OER catalysts. We demonstrated a TiB2 supported IrOx (IrOx/TiB2) catalyst synthesized via wet chemistry deposition without post heat treatment combines a mass activity towards OER with high conductivity. Its conductivity of ~30 S/cm2 is comparable to that of Vulcan carbon, and ~105 times that of the counterpart IrOx/W-TiO2 (W-TiO2 represents commercial tungsten doped TiO2 nanoparticles). Meanwhile, the IrOx/TiB2 catalyst shows a mass activity comparable to that of the counterpart IrOx/W-TiO2, twice that of commercial Ir black, and 50 times that of a commercial IrO2/TiO2 catalyst in acidic solution. Durability test showed that the Ir dissolution of the IrOx/TiB2 in acidic solution holding at 2 V for 100 hours is comparable to that of Ir black. Characterization of the IrOx/TiB2 showed small hydrous IrOx nanoparticles (1-2 nm) uniformly distributed on the surface of TiB2 nanoparticles (~58 nm) with an Ir content of ~33±7 wt%. Membrane electrode assembly evaluation on the IrOx/TiB2 catalyst is undergoing. The results will be reported and discussed. References (1) IEA, World Energy Outlook, 2022. https://iea.blob.core.windows.net/assets/830fe099-5530-48f2-a7c1-11f35d510983/WorldEnergyOutlook2022.pdf (accessed 2023-02-12).(2) Mittelsteadt, C. (Invited) Ir Strangelove: Or How I Learned to Stop Worrying and Embrace the PEM. ECS Meeting s 2022, MA2022-01, 1335-1335.(3) Seeking Alpha Home Page. https://seekingalpha.com/article/4399727-sibanye-should-benefit-from-hydrogen-wars-thanks-to-iridium-exposure (accessed 2023-02-12).(4) Böhm, D.; Beetz, M.; Gebauer, C.; Bernt, M.; Schröter, J.; Kornherr, M.; Zoller, F.; Bein, T.; Fattakhova-Rohlfing, D. Highly conductive titania supported iridium oxide nanoparticles with low overall iridium density as OER catalyst for large-scale PEM electrolysis. Applied Materials Today 2021, 24, 101134.(5) Pham, C. V.; Bühler, M.; Knöppel, J.; Bierling, M.; Seeberger, D.; Escalera-López, D.; Mayrhofer, K. J. J.; Cherevko, S.; Thiele, S. IrO2 coated TiO2 core-shell microparticles advance performance of low loading proton exchange membrane water electrolyzers. Appl. Catal. B‐Environ. 2020, 269, 118762.(6) Zhao, S.; Stocks, A.; Rasimick, B.; More, K.; Xu, H. Highly Active, Durable Dispersed Iridium Nanocatalysts for PEM Water Electrolyzers. J. Electrochem. Soc. 2018, 165, F82-F89.(7) Oakton, E.; Lebedev, D.; Povia, M.; Abbott, D. F.; Fabbri, E.; Fedorov, A.; Nachtegaal, M.; Copéret, C.; Schmidt, T. J. IrO2-TiO2: A high-surface-area, active, and stable electrocatalyst for the oxygen evolution reaction. ACS Catal. 2017, 7, 2346-2352.(8) Lewinski, K. A.; van der Vliet, D.; Luopa, S. M. NSTF advances for PEM electrolysis-the effect of alloying on activity of NSTF electrolyzer catalysts and performance of NSTF based PEM electrolyzers. ECS Trans 2015, 69, 893.

Proton exchange membrane (PEM) water electrolysis has become increasingly attractive due to the penetration of renewable energy (e.g, solar and wind). Hydrogen production from PEM water electrolysis is advantageous over other technologies due to its simple and clean nature. Membrane and electrode assemblies (MEAs) of PEM electrolyzers typically use iridium (Ir) as an anode catalyst and Pt as a cathode catalyst. Performance and durability of the MEAs play an essential role for the cost and viable commercialization of PEM water electrolysis. However, unlike the well-established MEA benchmarks of PEM fuel cells, the performance and durability of PEM electrolyzer MEAs have not been thoroughly studied. The objective of this work is to establish benchmark MEA performance and durability for PEM water electrolysis. For this purpose, a series of oxygen evolution reaction (OER) catalysts, which includes commercial Ir black and various Ir nanostructures, has been evaluated under test protocols established at Giner Inc. These approaches include high-voltage hold (>1.8 V), accelerated stress test (e.g., voltage cycling from 1.4 to 2.0 V), and constant low-current operations. The polarization curves of the MEAs will be obtained after each test. The morphology and structure of MEAs after durability tests will be characterized to correlate to their performance and durability. The established performance and durability may provide metrics and guidance to the community of PEM water electrolysis. Acknowledgement: The financial support is from the Department of Energy under the Contract Grant DE-SC0007471.

Even though the increasing penetration of solar photovoltaic (PV) energy into the electric grid can reduce the carbon emission of power generation, the intermittency and variability of renewable solar energy lead to frequent and steep ramping operations of conventional fossil fuel power plants. Hydrogen production via water electrolysis using solar power can serve as a controllable load and provide a short/long duration energy storage to mitigate the grid fluctuations (i.e., PV smoothing) and improve the resiliency of power grid. The generated green hydrogen will be further stored under high pressure for subsequent utilizations (e.g., hydrogen fuel cell electric vehicle refueling).Polymer electrolyte membrane (PEM) electrolyzer with high efficiency and quick dynamic response is used to generate hydrogen [1,2]. The capacity factors of PV field and PEM electrolyzer can affect the performance of PV smoothing on the cloudy day. Even though PEM electrolyzers directly producing high pressure hydrogen are more energy efficient than ambient pressure electrolyzers followed by mechanical compression, higher pressure leads to more undesired hydrogen back diffusion to the oxygen side, which causes lower hydrogen production efficiency, cell degradation, and safety risk of hydrogen explosion limit [3,4]. Optimal design and operation of electrolyzer under fluctuating solar power are formulated based on an integrated hydrogen-based energy storage system (renewable solar coupled with green hydrogen production and storage). Different PV smoothing scenarios as well as optimal size and operation conditions of the PEM electrolyzer are investigated.The high-fidelity dynamic model of a PEM electrolyzer cell/stack is established with consideration of two-dimensional (“through-plane” and “in-plane”) mass/heat transfer coupled with electrochemical kinetics. The electrochemical reactions are considered using Butler-Volmer kinetics with varying surface molar concentrations of components. Maxwell-Stefan diffusion equation is adopted to calculate the gas-phase species molar concentration in the backing and catalyst layers. Hydrogen permeation back through membrane is included with consideration of both diffusion and convective transports as a function of operational pressure.To evaluate the transient response of the PEM electrolyzer stack, real-time PV data based on an Orlando Utilities Commission (OUC) solar farm is smoothed using the developed power signal control algorithm. The optimal PV smoothing control algorithm and the electrochemical dynamic stack model show the effectiveness of hydrogen-based energy storage system in smoothing the PV signal to improve the grid stability and flexibility.[1] Kumar, S.S. and Himabindu, V., 2019. Hydrogen production by PEM water electrolysis–A review. Materials Science for Energy Technologies, 2(3), pp.442-454.[2] Götz, M., Lefebvre, J., Mörs, F., Koch, A.M., Graf, F., Bajohr, S., Reimert, R. and Kolb, T., 2016. Renewable Power-to-Gas: A technological and economic review. Renewable energy, 85, pp.1371-1390.[3] Trinke, P., Bensmann, B., Reichstein, S., Hanke-Rauschenbach, R. and Sundmacher, K., 2016. Hydrogen permeation in PEM electrolyzer cells operated at asymmetric pressure conditions. Journal of The Electrochemical Society, 163(11), p.F3164.[4] Scheepers, F., Stähler, M., Stähler, A., Rauls, E., Müller, M., Carmo, M. and Lehnert, W., 2020. Improving the efficiency of PEM electrolyzers through membrane-specific pressure optimization. Energies, 13(3), p.612.

Looking for alternative energy sources has been an inevitable trend since the oil crisis, and close attentioned has been paid to hydrogen energy. The proton exchange membrane (PEM) water electrolyzer is characterized by high energy efficiency, high yield, simple system and low operating temperature. The electrolyzer generates hydrogen from water free of any carbon sources (provided the electrons come from renewable sources such as solar and wind), so it is very clean and completely satisfies the environmental requirement. However, in long-term operation of the PEM water electrolyzer, the membrane material durability, catalyst corrosion and nonuniformity of local flow, voltage and current in the electrolyzer can influence the overall performance. It is difficult to measure the internal physical parameters of the PEM water electrolyzer, and the physical parameters are interrelated. Therefore, this study uses micro-electro-mechanical systems (MEMS) technology to develop a flexible integrated microsensor; internal multiple physical information is extracted to determine the optimal working parameters for the PEM water electrolyzer. The real operational data of local flow, voltage and current in the PEM water electrolyzer are measured simultaneously by the flexible integrated microsensor, so as to enhance the performance of the PEM water electrolyzer and to prolong the service life.

Low hydrogen permeability and high durability proton exchange membrane with three-dimensional acid-base crosslink structure for water electrolysis

Mathematical modeling of an integrated photovoltaic-assisted PEM water electrolyzer system for hydrogen production

Introducción The yearly increase in energy demand has encouraged the scientific community to find new sources of energy production without affecting the environment. Renewable technologies have become extremely popular due to the low greenhouse emissions and availability of natural energy sources (wind, sun, water, earth, tides, etc.), However, because of the intermittent energy generation from renewable sources, it is complex to rely on these technologies to guarantee the energy supply. Therefore, over the last decade, hydrogen has become increasingly studied as an energy carrier to replace current energy production technologies based on fossil fuels. Hydrogen can be easily coupled with other energy sources, increasing the efficiency of the systems. Nevertheless, hydrogen cannot be found in nature on its own and needs to be produced, currently, the most efficient method for green hydrogen generation is based on the electrolysis of water, this electrochemical process relies on the availability of water and the efficiency and correct selection of the electrolyser. Thus, this research evaluates the Alkaline and Proton Exchange Membrane (PEM) electrolysers for green hydrogen generation using water from hydroelectric power plants in Ecuador. Objetivos Evaluate Alkaline and PEM electrolysers for green hydrogen generation from hydroelectric power in Ecuador Método The methodology consists of a literature review of different brands of alkaline and PEM electrolysers selecting the ones with the highest efficiencies. For the analysis of data and information processing, quantitative methods were used. Finally, a sample of 9 hydroelectric plants was obtained for the study (Molino, Mazar, Agoyán, San Francisco, Pucará, La Península, Illuchi N 1, Illuchi N 2, Marcel Laniado). Principales resultados Different electrolyser manufacturers were analysed: Nel ASA producer of alkaline as well as PEM electrolysers, among them several models were evaluated NEL A 300, NEL A 485, NEL A 1000, NEL A 3880 with alkaline technology, and NEL MC 250, NEL M 5000 with PEM technology. H-TECH Electronic Co.Ltd with its model H-TEC HCS 10 using PEM technology. SIEMENS Energy, with its electrolyser technology PEM Silyzer 300 and McPhy with Mclyzer alkaline technology. All models were evaluated with the data from the 9 hydroelectric plants. Using technical data from the selected electrolysers and availability factor (90 %) from the hydroelectric plants, the potential of hydrogen production per year was calculated. The NEL A 3880 model with a system factor of 94% and a power of 14.7 MW displays the highest hydrogen production for alkaline technology, while the NEL MC 250, with an efficiency of 79% and 1 MW of power using PEM technology shows the highest hydrogen generation, these results are achieved for the Agoyan hydroelectric plant. Conclusiones The alkaline electrolysers show a better hydrogen generation capacity, achieving a total of 300 x 10e6 Kg of H2 per year with the NEL A 3880 model, in comparison with the PEM electrolyser technology that accounts for a maximum hydrogen production of 214 x 10e6 Kg of H2 per year. These results from the evaluation of the electrolysers show that it is feasible to establish a system for green hydrogen production based on hydroelectric power plants in Ecuador. The authors acknowledge the financial support received from the Universidad Técnica de Ambato and Dirección de Investigación y Desarrollo (DIDE) through the research project number PFICM28 “ANÁLISIS DE FACTIBILIDAD DE GENERACIÓN DE HIDRÓGENO VERDE MEDIANTE FUENTES DE ENERGÍA HIDROELÉCTRICA EN EL ECUADOR”.

Proton Exchange Membrane (PEM) water electrolyzers are pivotal to the transition toward carbon-neutral fuel production, offering a scalable solution for sustainable hydrogen generation. To meet commercial viability, these systems must operate reliably for over 50,000 hours. However, chemical degradation of the PEM remains a significant barrier to long-term durability. One proposed degradation pathway involves the formation of hydrogen peroxide at the cathode, facilitated by low electrode potentials, the presence of platinum, hydrogen, and crossover oxygen. Hydrogen peroxide can initiate Fenton’s reactions, producing radicals that attack vulnerable sites in the ionomer. These radicals may form within both the membrane and electrode regions, compromising material integrity. Additionally, the effects of degradation products—such as short-chain ionomer fragments and hydrogen fluoride—on other system components are not well understood. Overall, the mechanisms driving chemical degradation and the key influencing factors remain insufficiently characterized.The challenge is further compounded by the need to develop next-generation PEMs on timelines much shorter than the systems’ operational lifespans. This necessitates robust accelerated stress testing (AST) protocols to evaluate new materials and mitigation strategies for specific degradation modes. A clear understanding of the factors that accelerate chemical degradation and their relation to performance loss is critical for the design of meaningful AST protocols.In this study, we investigate the mechanisms of chemical degradation in PEM water electrolyzers using fluoride release and post-mortem characterization as key indicators. We examine the influence of environmental and operational parameters—including water quality, flow rate, pressure, and current density—on the degradation rate. Iron contamination, particularly in the form of FeCl₂, is identified as a dominant stressor, and an iron-doping-based AST protocol is developed. This work contributes to the rapid evaluation of PEM materials optimized for conductivity, gas crossover, and durability trade-offs, ultimately supporting the development of more robust and efficient PEM electrolyzer systems.