Proton Exchange Membrane Electrolyzer Emulator for Power Electronics Testing Applications

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

Evaluation of carbon-supported Pt and Pd nanoparticles for the hydrogen evolution reaction in PEM water electrolysers

Proton exchange membrane (PEM) water electrolysis offers significant potential for sustainable production of green hydrogen due to its high current density, superior hydrogen purity, and excellent conversion efficiency. However, widespread industrial implementation remains challenging because state-of-the-art oxygen evolution reaction (OER) catalysts heavily rely on iridium, a precious metal with limited global supply and high costs.1–4 Therefore, considerable research efforts have been dedicated to developing new catalysts requiring lower iridium loadings. Although PEM electrolysis typically operates at elevated temperatures (50-80°C),1 most studies assessing catalyst activity and stability have been performed at room temperature, and the limited available temperature-dependent studies primarily focus on alkaline environments.5,6 In this work, we have systematically investigated the temperature-dependent activity and stability of two representative Ir-based catalysts: a commercial IrO₂ catalyst and a supported core-shell Ir@IrOₓ catalyst. Using a high-temperature rotating-disk electrode (RDE) setup, electrochemical assessments of the activity and stability of the catalysts were performed across a range of operating temperatures from 20°C up to 80°C. We investigated how the increased operating temperature affects the OER activities of these two catalysts, observing not only enhanced kinetics with the increased working temperatures but also altered reaction mechanisms, as indicated by the Tafel analysis of the OER polarization curves. Furthermore, by employing an accelerated stress test protocol, we evaluated the stability of the two catalysts under varied temperatures. Comprehensive in-situ and post-mortem characterization techniques, including in-situ XRD, XPS (Figure 1), TEM, and ICP, were employed to investigate the structural changes of the catalysts during the stability tests, which revealed the accelerated degradation at higher working temperatures, but also the surprisingly high OER stability of the core-shell Ir@IrOx structure under high working temperatures.Figure 1: Comparison the Ir 4f XPS spectra of the sample before and after the stability test at 60 °C.References Carmo, M., Fritz, D. L., Mergel, J. & Stolten, D. A comprehensive review on PEM water electrolysis. Int J Hydrogen Energy 38, 4901–4934 (2013). Wang, C. & Feng, L. Recent advances and perspectives of Ir-based anode catalysts in PEM water electrolysis. Energy Advances 3, 14–29 (2024). Kibsgaard, J. & Chorkendorff, I. Considerations for the scaling-up of water splitting catalysts. Nature Energy 2019 4:6 4, 430–433 (2019). Reier, T., Oezaslan, M. & Strasser, P. Electrocatalytic oxygen evolution reaction (OER) on Ru, Ir, and pt catalysts: A comparative study of nanoparticles and bulk materials. ACS Catal 2, 1765–1772 (2012). Shi, G. et al. Temperature Dependence of Oxygen Evolution Reaction Activity in Alkaline Solution at Ni-Co Oxide Catalysts with Amorphous/Crystalline Surfaces. ACS Catal 12, 14209–14219 (2022). Lyu, X., Li, J., Yang, J. & Serov, A. Significance of slight ambient temperature variation on the electrocatalyst performance toward oxygen evolution reaction. J Environ Chem Eng 11, 111492 (2023). Figure 1

Electrolysis – Proton-exchange membrane electrolyzer | Proton exchange membrane water electrolysis: State-of-the-art technique and systems

This study presents exergetic assessment of a high-pressure hydrogen production system (HPS). The system considered in this study includes a high-pressure proton exchange membrane (PEM) electrolyzer, two heat exchangers, a motor pump system, a circulation pump, and a hot water tank. In order to perform the main objective of this study, the following important parameters are taken into consideration: (1) the operating pressure (ranging from 1 to 200 bar), (2) the operating temperature (ranging from 70 to 80 °C), (3) dead-state temperature (assumed to be 25 °C), (4) the energy efficiency of the PEM electrolyzer (ranging from 0.5 to 1), (5) the pump efficiency (assumed to be 0.8), (6) mass flow rate of hydrogen from PEM electrolyzer (3 kg per hour), and (7) mass flow rate of pure water supplied to the PEM electrolysis (27 per hour). Considering all these parameters, exergy analysis is performed for the HPS. The results show that exergy efficiency of HPS increases with the rise of the operating pressure and temperature. It thus requires a higher amount of energy input. In this regard, there is a strong need to optimize the process.

Electricity and hydrogen co-production via scramjet multi-expansion open cooling cycle coupled with a PEM electrolyzer

Polymer Electrolyte Membrane (PEM) electrolyzers as a promising technology in addressing climate change challenges and facilitating the development of renewable energy sources at lower costs. They offer clean operation and scalability, making them a valuable tool for harnessing energy without leaving any carbon footprint. However, a key challenge to widespread PEM electrolyzer adoption is the cost of the porous transport layer (PTL). In this study, we address this challenge by utilizing stochastic modeling to develop 3D PTL models numerically. To optimize the structural and transport properties of the PTL, we explored a range of combinations for the radius (2, 3, 4, 5 µm) and volumetric fraction (20%, 40%, 60%, 80%, 100%) of small fibers dispersed within a matrix of large fibers (6 µm) (Figure 1). The structural properties (e.g., mean surface roughness, specific surface area) were analyzed numerically, whereas transport properties (e.g., thermal conductivity, electrical conductivity, and diffusivity) were analyzed via pore network modeling. Before further analysis, our model was validated against both experimental and numerical results from previous research works. In our study, we observed that increasing the volumetric fraction of small fibers, while decreasing their radius, led to reduced surface roughness and higher thermal and electrical conductivity. However, this came at the cost of increased tortuosity, which hindered the diffusion and permeability of the material. Conversely, PTLs with a higher volumetric fraction of large fibers exhibited the opposite trend.By combining these insights, we developed customized multi-layer PTLs. These PTLs have a small fiber radius at the catalyst side and a large fiber radius at the flow-field side. This design leverages the advantages of both small and large fiber radii. Our customized multi-layer PTLs demonstrated improved gas removal, higher electrical conductivity, and better heat dissipation while maintaining good surface contact area and reduced roughness. To utilize the benefits of our modeled multi-layer PTL in an electrolyzer cell, the volumetric fractions of the fiber radius should be adjusted based on operating conditions. By tailoring the fiber characteristics and PTL geometries, we can develop optimized PTL models that can be scaled to real-time PEM electrolyzer setups for renewable energy generation, paving the way for a better future. Figure 1

Hydrogen is one of the most efficient energy carriers and can be produced by different methods. Among all the production methods, the proton exchange membrane water electrolyzer (PEMWE) is considered as the most promising technique to produce highly pure hydrogen from renewable energy sources with pure oxygen as by-products with no carbon emissions. The PEMWE technology has reached the early stages of commercial deployment while the mass production is tied to cost reduction. A PEMWE single cell comprises a membrane electrode assembly which considered as a core component where the electrochemical reactions take places in three phase boundaries. It also includes a titanium based porous transport layer (PTL) in anode side and carbon-based gas diffusion layer (GDL) in cathode side for the transportation of water and gas into and out of the cell. Additionally, bipolar plates (BPPs) with grooves provide mechanical support for the cell and distribute the water inside the cell and remove generated gases to the outlet trough flow field distribution channels. PTLs and BPPs, which are metallic components, are designed to endure the corrosive conditions present in the electrolyzer and they both needs protective coatings to stand at high voltage (<2 V), acidic media, temperature (60–80 °C) and oxygen saturated environment (anode).In this research, a modified electroplating process is used to deposit gold thin film as a protective film on both stainless steel (SS) and titanium based BPPs and PTLs, respectively. The electroplating of gold is a mature technology and easy to implement for large scale coating. This process will be impacted by many factors, such as the ingredient of plating solution, arrangement of electrodes, current distribution, and operating parameters. In addition, pre-treating the surface plays an important role to develop the durable thin films with proper adhesion. The gold striking underlayer on the SS substrate passivated the surface oxides and facilitated a dense electroplated chromium layer. Furthermore, a uniform gold protective layer was electroplated on the chromium coated substrate to achieve a promising anti-corrosive property. To evaluate the impact of pre-treatment and the anti-corrosion properties of the developed coating, different physical and electrochemical characterization techniques are conducted. As a result, The Au/Cr/Au coating on the SS substrate showed corrosion current density of 0.84 µA/cm2 and lower degradation as compared to without gold striking underlayer.The surface morphology and the crystallinity and phase analysis are investigated by scanning electron microscopy and X-ray diffraction (XRD), respectively. X-ray photoelectron spectroscopy (XPS) is used to study the surface properties and the bonds between the elements. The contact resistance also is studied under different pressures. In addition, traditional lab-scale durability analysis, using stagnant liquid electrolyte and three-electrode cell setups, might not provide such a precise information for PEM water electrolyzer. The three-electrode setup does not include crucial parameters relating to real cell-operating conditions or contributions to the PTL by other key cell components such as the membrane, catalyst layer, ionomer, and bipolar plates. Flow electrochemical setup is developed in our lab and is used to run the accelerate stress test to check the durability of the coated samples. Potentiodynamic, chronoamperometry and impedance also used to evaluate the samples. Figure 1. (a) Schematic of gold electroplating on the SS substrate, (b) SEM image and EDX analysis of Au/Cr/Au coating.We would like to acknowledge the support of the Natural Sciences and Engineering Research Council of Canada, Canada Research Chair and Mitacs Accelerate program and Intlvac Thin Film for their constant support. Figure 1

Polymer electrolyte membrane (PEM) electrolysis is widely considered a promising technology for energy storage and clean hydrogen production, due to the advantages it has over state-of-the-art alkaline water electrolysis.1 Typically, PEM electrolysers can operate at higher current densities than their alkaline counterparts, have a more robust design, and due to the zero-gap design, exhibit smaller Ohmic losses. Furthermore, PEM electrolysers can yield hydrogen at elevated pressures, eliminating the need for compression. Nevertheless, a series of challenges hinder the large-scale commercial implementation of PEM electrolysers. One of the most critical drawbacks is the need for noble metal electrocatalysts, especially at the anode of the cell, such as iridium or ruthenium, to catalyze the oxygen evolution reaction (OER) (1).2H2O → O2 + 4H+ + 4e- E° = 1.23 V vs NHE (1)These metals are used due to their high catalytic activity and long-term stability in the corrosive acidic environment of the PEM cells and their replacement by more available materials is difficult. Over the years, the main efforts of the scientific community towards solving this challenge were focused on increasing the noble metal dispersion, by using various high surface area catalyst supports, using core-shell catalysts, with the aim to minimize the amount of noble metal, modifying the morphology of the electrode, to improve mass transport limitations and electric contact between components and maximize noble metal utilization.2-4 Antimony-doped tin oxide has been reported as a stable OER catalyst support, offering sufficient electronic conductivity at the same, in order to minimize Ohmic losses.5 Furthermore, recent reports indicate that SnO2 does not only act as a catalyst support but takes part in catalysis.6 Building upon literature reports, we prepared a series of Sn/Ir OER catalysts by a two-step sodium borohydride reduction method, in which Sn nanoparticles were deposited over the surface of iridium black particles, decorating it. Catalysts with varying Sn content were incorporated in membrane electrode assemblies (MEAs) and their cell performance was evaluated in a single cell PEM electrolyser. We found that catalysts with up to 20 wt% tin content exhibited an improved cell performance compared to MEAs with similar iridium black loading. We modeled Ohmic, kinetic and mass transport overpotential contributions to experimentally acquired polarization curves and identified that the better cell performance arises mainly from the higher intrinsic catalytic activity, reflected by a higher apparent exchange current density of Sn/Ir OER catalysts compared to Ir black catalysts. The Sn/Ir MEAs also displayed lower mass transport overpotentials, which indicate improved transport in the catalyst layer. This can be due to a more porous structure and less agglomeration of iridium particles induced by the presence of tin over their surface.Interestingly, this performance improvement was only observed for iridium black catalysts. We prepared a series of IrO2-SnO2 catalysts by solution combustion synthesis method, which is known to yield high surface area disperse oxide materials. Comparing the performance of these catalysts to commercial iridium oxide catalysts in the PEM electrolysis cell, the MEAs with SnO2-containing catalysts displayed worse cell performance than MEAs with commercial iridium oxide. Modelling the overpotential contributions showed a lower apparent exchange current density, indicating a lower intrinsic catalytic activity of IrO2-SnO2 catalysts, as well as a higher Ohmic resistance, due to SnO2 addition. These observations indicate the importance of iridium oxidation state for harnessing the promotion effect of tin addition and give important insights into designing more efficient OER catalysts for PEM electrolysis cells.

Proton exchange membrane (PEM) water electrolysis is a technology designed to produce H2 using only water and electricity as inputs; it has gained increased attention in industry and academia due to its advantages over incumbent H2 generation processes (of which the most widely used are steam reforming and coal gasification) namely, low temperature, carbon-neutral and intermittent operation. PEM electrolysis can be instrumental for creating a hydrogen economy, although still much research needs to be carried out before widespread industrial adoption is achieved. PEM water electrolyzers suffer energy losses associated with the chemical reactions and the transport of charge and mass; of these phenomena, mass transport in PEM electrolyzers is the least understood subject, given the complex nature of the interaction of multiphase flows (mainly consisting of liquid water and evolved gases) through micrometric pores. The subject of multiphase flow in water electrolysis and its relationship with the mass transport phenomena in PEM water electrolysis has been a prevalent subject in the literature. Despite numerous attempts at pinpointing the relationship between mass transport overpotential and the operating parameters, there is no clear consensus about which transport mechanisms dominate, nor about how the component design of PEM electrolyzers affects the mass transport. While the effect of temperature and current density on mass transport losses has been extensively studied and is well understood, there are significantly fewer studies that focus on the effect of water flow and pressure. Both water flow and pressure have a direct effect on mechanisms such as bubble nucleation and two-phase flows that occur in the porous structures within a PEM electrolyzer (electrodes and porous transport layers, PTLs). In this work, I studied the effect of water flow and pressure on the mass transport phenomena in PEM electrolyzers. Chapters 1 and 2 provide an introduction to the topic as well as a description of the materials and experimental setups used. Chapter 3 of this thesis depicts the visualization and modeling of bubble nucleation in an operating PEM electrolyzer. I discovered that bubble detachment radii are largely independent of water flow and I identified two types of bubbles: bubbles that detach after reaching a critical size, and bubbles that fill up the pores of a PTL before detaching. Chapter 3 consists of the measurements I carried out regarding the transport of evolved gas through the water-filled pores of a PTL, where I observed that water flow severely impedes the gas transport through the pores and that such impediment is related to a shear stress exerted by the water flow on the pores. Chapter 5 shows the measuring of mass transport losses using electrochemical impedance spectroscopy (EIS) on an operating PEM electrolyzer; the results indicate that pressure and water flow affect the diffusion of gas in the electrode and that the mass transport overpotential depends on design parameters of the PEM electrolyzer, such as electrode thickness and hydrophobicity. Overall, I derived a theoretical framework based on the assumption that the evolved gas in a PEM electrolyzer permeates through the PTL after diffusing from the active sites to the bubble nucleation sites. Such framework, constructed on the basis of the models regarding gas transport in porous media, can be used to explain the mass transport loses in a PEM electrolyzer that arise from operating with increased water flows and pressures. The model I derived can be used in future work as a guideline to optimize the components of a PEM electrolyzer, in particular regarding the hydrophobicity and pore size distribution of PTLs as well as the composition of the catalyst ink to produce the electrodes. Moreover, this work can also be used to further understand the mass transport losses and optimize the operation of PEM electrolyzers to decrease the energy consumption of H2 generation.

Proton exchange membrane (PEM) electrolysis and anion exchange membrane (AEM) electrolysis are both able to directly produce high purity hydrogen from electricity and water. Key benefits of electrolysis using polymer membrane separators include a quick response rate, enabling load following, and ability to operate with high differential pressure. Operation under differential pressure allows for simultaneous electrolysis and electrochemical compression, simplifying overall system design. The development and stack integration of new, high performance electrolysis materials must include consideration of operating range and durability under differential pressure to maintain the technologic benefits. PEM electrolyzers are commercially available on the megawatt scale and produce hydrogen fuel that is increasingly cost competitive with fossil fuel in select parts of the world. Better utilization of low cost electricity from renewable energy (wind and solar) is one route to additional hydrogen cost reductions, for which a wide current operating range is beneficial. Thinner membranes, more active catalysts, and better electrode design enable high currents at acceptable cell efficiencies. Performance and durability data will be presented on state-of-the-art PEM electrolyzer materials operating under differential pressure. AEM electrolyzers are not currently commercially available, but promise membrane, catalyst, and balance of stack cost reductions. To begin to compete with PEM technology, performance and durability need to be improved. This work focuses on membrane stability under differential cell pressure and material integration into high performance AEM electrolyzers.

A power management strategy for a proton exchange membrane (PEM) electrolyzer connected to a wind turbine conversion system (WTCS) is proposed in this paper. It is based on the characterization of the wind turbine and the electrolyzer as well. With the aim to interface the WCTS and the PEM electrolyzer, a stacked interleaved DC-DC buck converter has been chosen due to its benefits for this application from output current ripple and reliability point of view. This converter is controlled so that it can have a dynamic faster than the wind turbine avoiding overvoltage during transients, which could damage the PEM electrolyzer. In order to assess the performance of the power management strategy, experimental tests have been carried out. The reported results demonstrate the correct behavior of the system during transient operation.

One of the factors leading to a decrease in the efficiency of polymer electrolyte membrane (PEM) electrolyzers is the blockage of water transport pathways through the porous transport layer (PTL). The oxygen bubbles generated from the electrochemical reaction at the catalyst layer accumulate in the PTL, impeding the transport pathways and reaction sites for the reactant water (1). An improved understanding of oxygen bubble accumulation and water transport behaviour in porous transport layers is essential to reduce mass transport losses in PEM electrolyzers. This study presents a method to stochastically generate a PTL composed of sintered titanium (Ti) powders and investigate the transport properties using pore network modeling. A microscale X-ray computed tomography (µ-CT) was performed for a sintered Ti powder PTL sample to obtain a 2D density map. The density map contains material content information, providing higher intensity at the positions with higher material content. With the density map as an input, a stochastic model of the PTL was generated by placing Ti powder particles at positions decided by the density map and a probability function until the model reached the target volume (2). Two critical parameters are considered in this model: the seeding parameter, α, and a filling radius, β. The seeding parameter controls the number of Ti powder “seeds” that act as nucleation sites. The second parameter, the filling radius, allows the model to mimic the morphology of the sintered regions. The structural properties of the stochastic model are investigated by comparing the pore size distribution, throat size distribution, and the porosity profile to the µ-CT reconstruction. Pore network modeling is an alternative to continuum modeling for simulating transport in porous media. Pore network modeling simplifies the solution of differential equations for mass transport by treating the pore space as a network of pores and narrow throats (3). Using pore network modeling as the analysis tool, the in-plane permeabilities of the µ-CT reconstruction and the stochastic model were compared. The stochastic modeling of PTLs will facilitate the detailed parametric studies of PTL structural property impacts on transport and provide novel insights into mass transport behavior in PEM electrolyzers.References H. Ito, T. Maeda, A. Nakano, Y. Hasegawa, N. Yokoi, C. M. Hwang, M. Ishida, A. Kato, and T. Yoshida, International journal of hydrogen energy 35(18), 9550-9560 (2010). A. Ebrahimi Khabbazi, J. Hinebaugh, A. Bazylak, Science Bulletin, 61(8), 601-611(2016).A. Putz, J. Hinebaugh, M. Aghighi, H. Day, A. Bazylak, and J. T. Gostick, ECS Transactions, 58(1), 79-86 (2013).

Physics-Informed Neural Network for modeling and predicting temperature fluctuations in proton exchange membrane electrolysis

Hydrogen production from proton exchange membrane (PEM) water electrolysis is attractive 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. The durability of MEAs plays an essential role for the electrolyzers’ lifetime and cost. However, unlike the well-established MEA durability protocols of PEM fuel cells, there have been a lack of effective procedures for PEM electrolyzer MEA durability evaluation. The objective of this work is to establish a series of test protocols that can help to rapidly evaluate PEM electrolyzer MEA durability. Three testing approaches have been used in this work, which include high-voltage hold (>1.8 V), voltage cycling (1.4 to 1.8 V or 2.0 V), and constant low-current operations. The electrochemical surface area (ECSA) and polarization curves of the MEAs will be obtained after each test. Two categories of anode catalysts have been evaluated using the above durability test protocols: one is the commercial Ir black and the other is Ir supported on tungsten-doped titanium oxide (Ir/WxTi1-xO2) developed at Giner. The supported Ir/WxTi1-xO2 catalyst proves to possess 8-10 x higher mass activity than the Ir black. The MEAs made of these two anode catalysts have been evaluated at a variety of loading, low (0.1 mg/cm2), medium (0.4 mg/cm2) and high (1.0 mg/cm2). Figure 1 shows the durability of these two catalysts after voltage cycling from 1.4 V to 1.8 V: (a) 2 mg/cm2 Ir from Ir black; (b) 0.4 mg/cm2 Ir from Ir/WxTi1-xO2. It can be seen that at medium to high Ir loadings, these two catalysts demonstrates minimal performance decay after voltage cycling. The morphology and structure of MEAs after durability tests will be characterized to correlate to their performance and to elucidate their degradation mechanisms. Acknowledgement: The financial support is from the Department of Energy under the Contract Grant DE-SC0007471. Figure 1