Polymer Electrolyte Fuel Cells Research Articles

Operando Scanning Small-/Wide-Angle X-ray Scattering for Polymer Electrolyte Fuel Cells: Investigation of Catalyst Layer Saturation and Membrane Hydration- Capabilities and Challenges.

Polymer electrolyte fuel cells are an essential technology for future local emission-free mobility. One of the critical challenges for thriving commercialization is water management in the cells. We propose small- and wide-angle X-ray scattering as a suitable diagnostic tool to quantify the liquid saturation in the catalyst layer and determine the hydration of the ion-conducting membrane in real operating conditions. The challenges that may occur in operando data collection are described in detail─separation of the anode and cathode, cell alignment to the beam, X-ray radiation damage, and the possibility of membrane swelling. A synergistic development of experimental setup, data acquisition, and data interpretation circumvents the major challenges and leads to practical and reliable insights.

Performance uniformity analysis in polymer electrolyte fuel cell using long-term dynamic simulation

The temporal stability and spatial homogeneity of current density are key factors in Polymer Electrolyte Fuel Cell (PEFC) performance and durability. Temporal and spatial variations of relative humidity, fuel concentration, and water droplets in the channels are the principal causes of non-homogeneous current density. A dynamic pseudo-3D model was previously proposed by the authors and has been extended and improved to perform the long-term and intensive simulations of PEFC with low computational cost, which allows to study of the performances homogeneity with different experimental configurations and flow field topologies. The model considers important phenomena in the homogeneity analysis, such as gases and liquid water movement in diffusion layers and flow field, electrochemical reactions, and others. Model validation has been performed using experimental data obtained from a 25 cm2 cell with a single serpentine, which has allowed studying the model transient response and spatial representation. The simulations have been used to study the homogeneity and stability of 36 setups of PEFC, varying the rib/channel width ratio, the stoichiometric ratio, and the number of parallel serpentine channels. The results show the importance of a properly flow field design to control gas flow, remove the channels’ liquid water, and keep a homogeneous feeding. The study evaluated a set of channel configurations that show the improved temporal voltage stability and current density spatial homogeneity. The results show the impact of channel gas speed and ratio channel/rib width in liquid droplets removal and the proper fuel spatial distribution; and how configurations with a lesser number of channels in serpentine design require a lower stoichiometric ratio to perform better temporal and spatial uniformity. In the case of the cell configurations simulated, the optimum design was achieved using between 5 and 7 parallel serpentine channels and a channel/rib ratio 3/5.

Pt nanorods supported on Nb-doped ceria: A promising anode catalyst for polymer electrolyte fuel cells

For polymer electrolyte fuel cells (PEFCs), platinum nanoparticles supported on carbon black (Pt/C) serve as the commonly used hydrogen anode catalyst, exhibiting high activity for the hydrogen oxidation reaction (HOR), while the carbon support is susceptible to corrosion under PEFC operation. Here, a highly active HOR anode catalyst of Pt nanorod supported on niobium (Nb)-doped ceria without using corrosive carbon support was developed, which exhibits high durability at high potentials associated with hydrogen starvation. The production of hydrogen peroxide (H2O2), which can degrade the polymer electrolyte membrane, was also found to be significantly suppressed on the Pt nanorod/doped ceria catalyst. Density functional theory (DFT) calculations suggests that the Pt nanorod geometry and interaction with Nb and Ce favor HOR activity and stability while suppressing H2O2 production by modulating the adsorption of key reaction intermediates. This new catalyst has the potential to be used as an anode for high-performance and high-durability PEFCs.

Multiscale characterization of polymer electrolyte fuel cells elucidated by quantum beam analysis

Abstract Polymer electrolyte fuel cells (PEFCs) offer promising alternatives to conventional gasoline engines in automobiles and have been commercialized over the past decade. This progress can be attributed to state-of-the-art materials with high performance, long-term durability, and robust manufacturing technologies. The multiscale hierarchical structure inherent in PEFCs facilitates the transfer of protons, electrons, oxygen, and water. As various phenomena in PEFCs occur at different scales, multiscale analysis, including quantum beam analysis, is of great interest for materials development and for understanding the processes that take place in PEFCs. In particular, advancements in this field have enabled the further tailoring of properties in a controlled manner and the design of nanostructures processing superior material properties. Additionally, the expansion of quantum beam sources has facilitated the study of manufacturing protocols. This review presents the achievements in the use of synchrotron x-ray and neutron sources in the field of PEFCs, while also addressing remaining issues for the widespread commercialization of fuel cell electric vehicles.

Adaptability of Heteropolytungstate Anions as Efficient Anode Redox Mediators in Redox Flow Polymer Electrolyte Fuel Cells.

Heteropolyanions (HPAs) are known as the candidate for an anode redox mediator for redox flow polymer electrolyte fuel cells (PEFCs). The electrochemical properties of HPAs differ depending on the transition elements and heteroatoms in HPAs. For example, heteropolytungstate anions (W-HPAs), in which the transition element is tungsten, have a lower one-electron reduction potential than other HPAs. Therefore, it has been reported that redox flow PEFCs adapted with W-HPAs exhibit high power generation performance. On the other hand, studies on the heteroatoms of HPAs are limited only to electrochemical properties, and statistical and comprehensive studies on the power generation performance of redox flow PEFCs are lacking. Thus, it is beneficial to clarify the optimal heteroatom in order to design anolytes suitable for redox flow PEFCs. In this study, heteropolytungstate anions with different heteroatoms were adapted as anodic redox mediators in a redox flow PEFC. In power generation tests, the redox flow PEFC with an anolyte of zinctungstate anion showed the highest performance. Zinctungstate anion exhibited the fastest reduction and oxidation rates among the W-HPAs investigated in this study.

Effects of Humidity and Produced Water on Specific Adsorption of High Oxygen Permeability Ionomers Composed Entirely of Cyclic Monomers on Cathode Performance for Polymer Electrolyte Fuel Cells

Effects of Humidity and Produced Water on Specific Adsorption of High Oxygen Permeability Ionomers Composed Entirely of Cyclic Monomers on Cathode Performance for Polymer Electrolyte Fuel Cells

Water management and mass transport of a fractal metal foam flow-field based polymer electrolyte fuel cell using operando neutron imaging

Metal foam flow-fields (MFFs) exhibit immense potential for enhancing the performance of polymer electrolyte fuel cells (PEFCs) owing to their advantageous pore connectivity and abundant gas pathways. Nevertheless, challenges remain with the conventional MFF concerning reactant homogeneity and water management. To address these concerns, this study incorporates a fractal manifold into the MFF design. By employing operando neutron imaging, device-level testing, and electrochemical impedance spectroscopy (EIS), a comprehensive understanding of mass transfer and water management characteristics across the fractal manifold MFF is obtained. This novel design delivers better cell performance and lower mass transport resistance compared to the conventional MFF under all experimental conditions investigated. Notably, neutron imaging reveals that the fractal manifold MFF consistently exhibits a reduced liquid water content and more uniformly distributed liquid water compared to the conventional MFF. These superior characteristics of the design contribute to a substantial ∼15% increase in maximum power density compared to the conventional MFF-based PEFC. The results indicate the potential for further performance improvement by optimizing manifold parameters.

Local oxygen transport resistance in polymer electrolyte fuel cells: origin, dependencies and mitigation

Next-generation polymer electrolyte fuel cells (PEFCs) require an integral design of the porous structure of electrodes at different scales to improve performance and enlarge durability while reducing cost. One of today’s biggest challenges is the stable, high-performance operation at low Pt loading due to the detrimental effect of the local oxygen transport resistance caused by ionomer around catalyst sites. Hindered local oxygen transport arises from sluggish kinetics at the local reaction environment, that comprises adsorption at (wet) ionomer and Pt interfaces, and diffusivity of gas species in ionomer and water. Diverse factors affect oxygen transport, including operating conditions (relative humidity, temperature, and pressure), ionomer content and morphology, ionomer heterogeneity, porosity of carbon support, catalyst dispersity, and flooding. To attain performance and durability targets, it is essential to maximize the oxygen utilization of the catalyst layer by implementing enhanced membrane electrode assembly architectures. This involves employing advanced catalyst layer preparation techniques, including electrospraying, to generate optimized highly porous morphologies. Furthermore, achieving these targets necessitates the development of new materials with tailored properties, such as high permeability and porous ionomers, among other innovative strategies.

Understanding water dynamics in operating fuel cells by operando neutron tomography: investigation of different flow field designs

Water management plays a key role in ensuring optimum polymer electrolyte fuel cell (PEFC) performance, and flow field design can influence the ability of a cell to balance maintaining hydration, whilst avoiding flooding and cell failure. This work deepens the understanding of water evolution in different PEFC flow channel designs, namely single serpentine (SS), double serpentine (DS) and parallel, using our novel high-speed neutron computed tomography method. We developed our previously-reported method by introducing continuous cell rotation, enabling 18 s per tomogram during 1 h holds at 300, 400 and 500 mA cm−2. The volume of water evolved in the cathode, membrane electrode assembly and anode was quantified, and key mechanisms for water droplet formation in the different flow channel designs were elucidated. The parallel flow field design had the poorest water management, with 47% of the cathode flow channel becoming filled after 1 h at 400 mA cm−2. This significant flooding blocked reactant sites and contributed to unstable cell performance and, ultimately, cell failure at higher current densities. The SS cell displayed the best water management, with only 11% of the cathode channel filled with water after 1 h at 500 mA cm−2, compared with 28% of the DS cathode channel. 3D visualisation and analysis of droplet behaviour elucidated how water ‘slugs’ in the SS were removed in the gas stream, whereas three of the four parallel cathode flow channels became entirely filled with water plugs, blocking gas flow and exacerbating cell flooding. The new insights gained here are expected to extend to novel flow field designs and image-based models, with the use of operando neutron CT demonstrated as a powerful technique for both visualising and quantifying water management in operating PEFCs, as well as deepening the knowledge of droplet behaviour in different flow field types.

Non-Invasive Measurement of Impedance Spectra Distribution in Polymer Electrolyte Fuel Cells

Localized measurement of the impedance distribution in an operating polymer electrolyte fuel cell stack is of great importance in providing information on its state of health and performance. However, the current methods’ invasiveness is a brake to a more widespread utilization. This work presents a non-invasive way to measure and interpret local impedance spectra. It is based on local AC current supply and local voltage measurements performed all around the cell via conductive pins contacting the outer surface of the flow fields. The different local spectra are measured on a single cell within a 200 cm2 six-cell stack under different operation conditions and compared to a reference case with homogeneous current density. A simple equivalent electrical circuit is used to fit the impedance spectra and to extract membrane and charge transfer resistance. The variations of these two values are analyzed at five different positions along the channel for different cathode stoichiometries and gas flow configurations.

Study on the Relationship between GDL Wettability and Liquid Water Behavior in Polymer Electrolyte Fuel Cells

Liquid water that accumulates inside gas diffusion layers (GDL) prevents oxygen transport and degrades the performance of polymer electrolyte fuel cells (PEFCs). Therefore, improving the drainage of GDL is neccesary. One factor that directly affects drainage is the wettability of GDLs. In this study, the relationship between wettability of GDL and drainage was investigated through a numerical simulation using the volume of fluid (VOF) method. The simulation incorporated condensation model to mimic the actual operation of a PEFC. As a result of the simulation, it was found that condensation occurs near the catalyst layer (CL), and that liquid water accumulation develops from the vicinity of the CL side to the channel side. Simulations for different contact angles of θ contact = 60°, 90°, 110°, and 150° were performed, and showed that the liquid water volume inside the GDL decreased in the case of higher contact angle. In addition, we found that the hydrophobicity of the GDL promotes the movement of liquid water and hastened liquid-water discharge from the GDL surface. In the case of higher contact angle, the proportion of the gas-liquid interface in the GDL and its curvature were found to increase. Furthermore, the liquid water was discharged from greater number of pores on the GDL surface.

Probing multiphase reactive transport interactions in the polymer electrolyte fuel cell catalyst layer degradation

The multiphase, multicomponent reactive transport plays a critical role in the degradation of the cathode catalyst layer in Polymer Electrolyte Fuel Cells. This warrants a fundamental understanding of the pore-scale, mechanistic interactions in the catalyst layer. Herein, the interfacial and transport interactions due to the flooding dynamics in the presence of carbon support corrosion, which is a primary degradation mode in the cathode catalyst layer, are delineated based on a comprehensive mesoscale model. The mechanistic interrogation of the degradation-transport interactions reveals the spatio-temporal heterogeneity of the pristine and aged microstructures. An electrode-averaged saturation front of 80 % unveils a critical limit of percolation which results in an onset of limiting current density. Further, it is observed that the reactant severity is amplified at progressively higher stages of corrosion owing to the appearance of dead pores and a thicker ionomer film. We also shed light on the fluid displacement patterns which reveal the existence of a capillary fingering regime. The interplay of the operating current density and carbon corrosion in governing the substrate-ionomer interaction is described through an electrochemical Damköhler number.

Quantitative observation of water phase transition in gas diffusion layers utilizing advanced in situ differential scanning calorimetry

The study investigates the freezing behavior of supercooled water in gas diffusion layers (GDLs) of polymer electrolyte fuel cells (PEFCs). Using an innovative advanced in situ differential scanning calorimetry (advanced DSC) technique, we analyze phase transitions within GDLs at a single-cell scale, excluding impacts of catalyst layers and membranes. This method overcomes the limitations of traditional DSC, allowing variable water saturation and distribution. We find that freezing-thawing and drying-saturating cycles contribute to noticeable variations in the freezing temperature (Tonset) of supercooled water, ranging from −6 °C to −15 °C, attributed to the heterogeneous surface of GDL and water redistribution. Repeated drying-saturating cycles remove nucleation seeds, lowering the freezing point of water − a "cleaning effect." The freezing probability reduces at lower saturation levels, influenced by waterproof treatment uniformity on GDLs. Residual ice can be detrimental to the cold-start capability of PEFCs, as it promotes freezing of supercooled water around −1 °C. Our findings enhance understanding of water behavior in GDLs and its impact on PEFC cold-start performance. Applying this technique to other cell components, such as the catalyst layer, could further elucidate water freezing dynamics in PEFCs and guide the innovation of more reliable cell components for PEFC applications in broader climates.

Development of Pt Nanosheets toward Polymer Electrolyte Fuel Cells

Development of Pt Nanosheets toward Polymer Electrolyte Fuel Cells

Enhanced fault detection in polymer electrolyte fuel cells via integral analysis and machine learning

The growing energy demand and population raising require alternative, clean, and sustainable energy systems. During the last few years, hydrogen energy has proven to be a crucial factor under the current conditions. Although the energy conversion process in polymer electrolyte fuel cells (PEFCs) is clean and noiseless since the only by-products are heat and water, the inside phenomena are not simple. As a result, correct monitoring of the health situation of the device is required to perform efficiently. This paper aims to explore and evaluate the machine learning (ML) and deep learning (DL) models for predicting classification fault detection in PEFCs. It represents a support for decision-making by the fuel cell operator or user. Seven ML and DL model classifiers are considered. A database comprising 182,156 records and 20 variables arising from the fuel cell's energy conversion process and operating conditions is considered. This dataset is unbalanced; therefore, techniques to balance are applied and analyzed in the training and testing of several models. The results showed that the logistic regression (LR), k-nearest neighbor (KNN), decision tree (DT), random forest (RF), and Naive Bayes (NB) models present similar and optimal trends in terms of performance indicators and computational cost; unlike support vector machine (SMV) and multi-layer perceptron (MLP) whose performance is affected when the data is balanced and even presents a higher computational cost. Therefore, it is a novel approach for fault detection analysis in PEFC that combines the interpretability of different ML and DL algorithms while addressing data imbalance, so common in the real world, using resampling techniques. This methodology provides clear information for the model decision-making process, improving confidence and facilitating further optimization; in contrast to traditional physics-based models, paving the way for data-driven control strategies.

Synthesis of a Mesoporous SnO2 Catalyst Support and the Effect of Its Pore Size on the Performance of Polymer Electrolyte Fuel Cells.

The aim of this study was to clarify the effectiveness and challenges of applying mesoporous tin oxide (SnO2)-based supports for Pt catalysts in the cathodes of polymer electrolyte fuel cells (PEFCs) to simultaneously achieve high performance and high durability. Recently, the focus of PEFC application in automobiles has shifted to heavy-duty vehicles (HDVs), which require high durability, high energy-conversion efficiency, and high power density. It has been reported that employing mesoporous carbon supports improves the initial performance by mitigating catalyst poisoning caused by sulfonic acid groups of the ionomer as well as by reducing the oxygen transport resistance through the Pt/ionomer interface. However, carbon materials in the cathode can degrade oxidatively during long-term operation, and more stable materials are desired. In this study, we synthesized connected mesoporous Sb-doped tin oxides (CMSbTOs) with controlled mesopore sizes in the range of 4-11 nm and tested their performance and durability as cathode catalyst supports. The CMSbTO supports exhibited higher fuel cell performance at a pore size of 7.3 nm than the solid-core SnO2-based, solid-core carbon, and mesoporous carbon supports under dry conditions, which can be attributed to the mitigation of the formation of the Pt/ionomer interface and the better proton conductivity within the mesopores even at the low-humidity conditions. In addition, the CMSbTO supports exhibited high durability under oxidative conditions. These results demonstrate the promising applicability of mesoporous tin oxide supports in PEFCs for HDVs. The remaining challenges, including the requirements for improving performance under wet conditions and stability under reductive conditions, are also discussed.

Experimental visualization of water/ice phase distribution at cold start for practical-sized polymer electrolyte fuel cells

The automotive industry aims to ensure the cold-start capability of polymer electrolyte fuel cells (PEFCs) for developing fuel cell electric vehicles that can be driven in cold climates. Water and ice behavior is a key factor in maintaining this capability. Previously reported methods for visualizing water and/or ice are limited to small-sized PEFCs ( < 50 cm2), while fuel cell electric vehicles are equipped with larger PEFCs. Here, we developed a system using a pulsed spallation neutron beam to visualize water distribution and identify water/ice phases in practical-sized PEFCs at a cold start. The results show direct evidence of a stepwise freezing behavior inside the PEFC. The produced water initially accumulated at the center of the PEFC and then froze, followed by PEFC shutdown as freezing progressed. This study can serve as a reference to guide the development of cold-start protocols, cell design, and materials for next-generation fuel cell electric vehicles.

Patterned hydrophobic gas diffusion layers for enhanced water management in polymer electrolyte fuel cells

Flooding of the cathode due to water accumulation is one of the biggest limiting factors in the performance of polymer electrolyte fuel cells (PEFCs). This study therefore attempts to solve this issue by fabricating gas diffusion layers (GDLs) with differently patterned hydrophobic regions. The GDLs in three different patterns (triangular, diamond, and inverted-triangular) were prepared by brushing a Polytetrafluoroethylene (PTFE) solution onto commercial carbon papers through a mask and tested in PEFCs. The patterned GDLs results in superior performance in all cases compared to a uniformly PTFE-treated GDL. Notably, the oxygen transport resistance is significantly reduced, indicating that the water accumulation in the cathode is avoided. This is attributed to the patterned hydrophobicity gradient providing distinct pathways for water and oxygen. The GDL with triangular patterning displays the highest peak power density, due to the fact that the untreated less hydrophobic region is in direct contact with the cathode outlet in this case, facilitating the removal of excess liquid water. Overall, the study confirms that the GDLs with patterned hydrophobicity could be used to enhance the performance of commercial PEFC systems by facilitating water management, potentially leading to improved efficiency and durability.

Highly Proton Conductive Membranes Based on Poly(vinylphosphonic acid)-Coated Cellulose Nanocrystals and Cellulose Nanofibers for Polymer Electrolyte Fuel Cells

Highly Proton Conductive Membranes Based on Poly(vinylphosphonic acid)-Coated Cellulose Nanocrystals and Cellulose Nanofibers for Polymer Electrolyte Fuel Cells

A Comprehensive Analysis of the Overpotential Losses in Polymer Electrolyte Fuel Cells

A Comprehensive Analysis of the Overpotential Losses in Polymer Electrolyte Fuel Cells