Numerical modeling of liquid water motion in a polymer electrolyte fuel cell

A three dimensional transient model fully coupling the two phase flow, species transport, heat transport, and electrochemical processes is developed to investigate the liquid water formation and transport in a polymer electrolyte fuel cell (PEFC). This model is based on the multiphase mixture (M2) formulation with a complete treatment of two phase transport throughout the PEFC, including gas channels, enabling modeling the liquid water motion in the entire PEFC. This work particularly focuses on the liquid water accumulation and transport in gas channels. It is revealed that the liquid water accumulation in gas channels mainly relies on three mechanisms and in the anode and cathode may rely on different mechanisms. The transport of liquid water in the anode channel basically follows a condensation–evaporation mechanism, in sharp contrast to the hydrodynamic transport of liquid water in the cathode channel. Liquid water in the cathode channel can finally flow outside from the exit along with the exhaust gas. As the presence of liquid water in gas channels alters the flow regime involved, from the single phase homogeneous flow to two phase flow, the flow resistance is found to significantly increase.     

X-ray imaging of water distribution in a polymer electrolyte fuel cell

At present, water management in a polymer electrolyte fuel cell (PEFC) is a major subject of research. In fact, proper water management is vital to achieve maximum performance and durability from a PEFC. Consequently, this study is conducted to visualize quantitatively the water distribution in a PEFC by means of an X-ray imaging technique. The X-ray images of the PEFC components with and without water are clearly distinguished. Reference to the visualized X-ray images, enables quantitative evaluation of the water distribution in the region between the separator and the gas-diffusion layer (GDL). Likewise, the meniscus of water in the channels of the PEFC is clearly observed.     

Performance equations for a polymer electrolyte membrane fuel cell with unsaturated cathode feed

A mathematical formulation for the cathode of a membrane electrode assembly of a polymer electrolyte membrane fuel cell is proposed, in which the effect of unsaturated vapor feed in the cathode is considered. This mechanistic model formulates the water saturation front within the gas diffusion layer with an explicit analytical expression as a function of operating conditions. The multi-phase flows of gaseous species and liquid water are correlated with the established capillary pressure equilibrium in the medium. In addition, less than fully hydrated water contents in the polymer electrolyte and catalyst layers are considered, and are integrated with the relevant liquid and vapor transfers in the gas diffusion layer. The developed performance equations take into account the influences of all pertinent material properties on cell performance using first principles. The mathematical approach is logical and concise in terms of revealing the underlying physical significance in comparison with many other empirical data fitting models.     

Numerical evaluation of various thermal management strategies for polymer electrolyte fuel cell stacks

Thermal management is one of the key factors required to ensure good performance polymer electrolyte fuel cell (PEFC) stacks. The choice of the thermal management strategy depends on the specific application, size, weight, design, complexity, and cost. In this work, we investigate various alternative thermal management strategies for PEFC stacks, e.g., forced convection in specially design cooling plate/channel with either (i) liquid or (ii) air as the coolant; (iii) edge-air cooling with fins and; combine oxidant and coolant flow (open-cathode) with (iv) forced and (v) natural convection air cooling. A three-dimensional two-phase model, comprising of the equations of conservation of mass, momentum, species, energy and charge, is employed to quantify the performance of various cooling strategies. The results demonstrate that thermal management is essential to ensure good stack performance. Liquid cooling, as expected, performs the best compared to air cooling, whereas natural convection cooling is just marginally able to maintain a stack with large number of cells from steep drop in performance. Finally, results presented in this paper can provide useful design guidelines for selection of a suitable thermal management strategy for a PEFC stack and its near-to- or optimum cooling condition.     

Dynamic water management of polymer electrolyte membrane fuel cells using intermittent RH control

A novel method of water management of polymer electrolyte membrane (PEM) fuel cells using intermittent humidification is presented in this study. The goal is to maintain the membrane close to full humidification, while eliminating channel flooding. The entire cycle is divided into four stages: saturation and de-saturation of the gas diffusion layer followed by de-hydration and hydration of membrane. By controlling the duration of dry and humid flows, it is shown that the cell voltage can be maintained within a narrow band. The technique is applied on experimental test cells using both plain and hydrophobic materials for the gas diffusion layer and an improvement in performance as compared to steady humidification is demonstrated. Duration of dry and humid flows is determined experimentally for several operating conditions.     

Quantitative visualization of temporal water evolution in an operating polymer electrolyte fuel cell

Synchrotron X-ray radiography is employed to visualize the temporal evolution of water inside the gas diffusion layer (GDL) of an operating (in situ) polymer electrolyte fuel cell (PEFC). A single-cell PEFC test kit is specially designed for the convenient capture of X-ray images. X-ray images of water in the PEFC components, such as the polymer membrane, GDL, and end plate, are captured consecutively. The synchrotron X-ray radiography of high-spatial and high-temporal resolution is suitable for observing the transport of a liquid layer and for visualizing water distribution inside the PEFC. As a result, the spatial distribution of water in the PEFC components is clearly and quantitatively visualized. The temporal evolution of water in the anode GDL due to back diffusion effect is clearly observed by adopting the image normalization method. The water-saturation characteristics at the cathode GDL, including saturation time and speed, are quite different from those at the anode GDL.     

Performance of membrane electrode assemblies using PdPt alloy as anode catalysts in polymer electrolyte membrane fuel cell

Pd-based nanoparticles, such as 40 wt.% carbon-supported Pd₅₀Pt₅₀, Pd₇₅Pt₂₅, Pd₉₀Pt₁₀ and Pd₉₅Pt₅, for anode electrocatalyst on polymer electrolyte membrane fuel cells (PEMFCs) were synthesized by the borohydride reduction method. PdPt metal particles with a narrow size distribution were dispersed uniformly on a carbon support. The membrane electrode assembly (MEA) with Pd₉₅Pt₅/C as the anode catalyst exhibited comparable single-cell performance to that of commercial Pt/C at 0.7 V. Although the Pt loading of the anode with Pd₉₅Pt₅/C was as low as 0.02 mg cm⁻², the specific power (power to mass of Pt in the MEA) of Pd₉₅Pt₅/C was higher than that of Pt/C at 0.7 V. Furthermore, the single-cell performance with Pd₅₀Pt₅₀/C and Pd₇₅Pt₂₅/C as the anode catalyst at 0.4 V was approximately 95% that of the MEA with the Pt/C catalyst. This indicated that a Pd-based catalyst that has an extremely small amount of Pt (only 5 or 50 at.%) can be replaced as an anode electrocatalyst in PEMFC.     

Two-phase modeling of gas purge in a polymer electrolyte fuel cell

Gas purge intended to minimize residual water in a polymer electrolyte fuel cell (PEFC) is critical for successful shutdown and sub-zero startup. In the present work, we present a two-phase transient model describing water removal from PEFC under gas purge conditions. The role of back diffusion from the cathode to anode along with liquid water transport in the gas diffusion layers behind the drying front and vapor diffusion ahead of the drying front is highlighted. The underlying ineffectiveness of cathode-only purge is outlined. The model predictions are compared with experimental results under various purge conditions. A good match with experiments is obtained at higher purge temperatures whereas some differences in the HFR profile is observed at lower temperatures. The role of drying front morphology in addressing the observed differences between numerical and experimental results is hypothesized.     

Microporous layer coated gas diffusion layers for enhanced performance of polymer electrolyte fuel cells

The influence of microporous layer (MPL) design parameters for gas diffusion layers (GDLs) on the performance of polymer electrolyte fuel cells (PEFCs) was clarified. Appropriate MPL design parameters vary depending on the humidification of the supplied gas. Under low humidification, decreasing both the MPL pore diameter and the content of polytetrafluoroethylene (PTFE) in the MPL is effective to prevent drying-up of the membrane electrode assembly (MEA) and enhance PEFC performance. Increasing the MPL thickness is also effective for maintaining the humidity of the MEA. However, when the MPL thickness becomes too large, oxygen transport to the electrode through the MPL is reduced, which lowers PEFC performance. Under high humidification, decreasing the MPL mean flow pore diameter to 3 μm is effective for the prevention of flooding and enhancement of PEFC performance. However, when the pore diameter becomes too small, the PEFC performance tends to decrease. Both reduction of the MPL thickness penetrated into the substrate and increase in the PTFE content to 20 mass% enhance the ability of the MPL to prevent flooding.     

Experimental study on enhancing the fuel efficiency of an anodic dead-end mode polymer electrolyte membrane fuel cell by oscillating the hydrogen

This paper investigates how to improve the fuel efficiency of an anodic dead-end mode fuel cell for portable power generation. Generally, a periodic purge process in anodic dead-end operation is required to avoid anode flooding caused by back diffusive water from the cathode. However, during the purge process, small amounts of the hydrogen are discharged with the water, lowering the fuel utilization efficiency. Therefore, hydrogen pulsations are introduced and experimental attempt to minimize the purge frequency is conducted in this study. The experimental results indicate that pulsation reduces partial pressure of the water vapor in the anode channel, increasing the interval between purges by approximately three times, thus improving overall efficiency.     

Investigation of freeze/thaw durability in polymer electrolyte fuel cells

This study aims to investigate the effect of different gas diffusion layers (GDLs) on freeze/thaw condition durability in polymer electrolyte fuel cells (PEFCs). Three kinds of GDLs–cloth, felt and paper type—with similar basic properties except thickness and bending stiffness were used. The changes in the properties and cell performance were investigated from the −30 to 70 °C range of freeze/thaw cycles. The I–V performance degradation was observed to be negligible for the felt GDL whereas the cloth and paper GDLs showed a marked I–V performance loss. No distinctive correlation between the changes in electrochemical properties, such as active metal surface area, hydrogen crossover rates and decreased I–V performance, was observed except an increase in ohmic resistance revealed by ac-impedance spectroscopy. The physical destruction of electrodes was also shown by scanning electron microscope (SEM) analysis.     

A lumped parameter model of the polymer electrolyte fuel cell

A model of a polymer electrolyte fuel cell (PEFC) is developed that captures dynamic behaviour for control purposes. The model is mathematically simple, but accounts for the essential phenomena that define PEFC performance. In particular, performance depends principally on humidity, temperature and gas pressure in the fuel cell system. To simulate accurately PEFC operation, the effects of water transport, hydration in the membrane, temperature, and mass transport in the fuel cells system are simultaneously coupled in the model. The PEFC model address three physically distinctive fuel cell components, namely, the anode channel, the cathode channel, and the membrane electrode assembly (MEA). The laws of mass and energy conservation are applied to describe each physical component as a control volume. In addition, the MEA model includes a steady-state electrochemical model, which consists of membrane hydration and the stack voltage models.     

A review of polymer electrolyte membrane fuel cell stack testing

This paper presents an overview of polymer electrolyte membrane fuel cell (PEMFC) stack testing. Stack testing is critical for evaluating and demonstrating the viability and durability required for commercial applications. Single cell performance cannot be employed alone to fully derive the expected performance of PEMFC stacks, due to the non-uniformity in potential, temperature, and reactant and product flow distributions observed in stacks. In this paper, we provide a comprehensive review of the state-of-the art in PEMFC testing. We discuss the main topics of investigation, including single cell vs. stack-level performance, cell voltage uniformity, influence of operating conditions, durability and degradation, dynamic operation, and stack demonstrations. We also present opportunities for future work, including the need to verify the impact of stack size and cell voltage uniformity on performance, determine operating conditions for achieving a balance between electrical efficiency and flooding/dry-out, meet lifetime requirements through endurance testing, and develop a stronger understanding of degradation.     

Prevention of the water flooding by micronizing the pore structure of gas diffusion layer for polymer electrolyte fuel cell

In polymer electrolyte fuel cells, high humidity must be established to maintain high proton conductivity in the polymer electrolyte. However, the water that is produced electrochemically at the cathode catalyst layer can condense in the cell and cause an obstruction to the diffusion of reaction gas in the gas diffusion layer and the gas channel. This leads to a sudden decrease of the cell voltage. To combat this, strict water management techniques are required, which usually focus on the gas diffusion layer. In this study, the use of specially treated carbon paper as a flood-proof gas diffusion layer under extremely high humidity conditions was investigated experimentally. The results indicated that flooding originates at the interface between the gas diffusion layer and the catalyst layer, and that such flooding could be eliminated by control of the pore size in the gas diffusion layer at this interface.     

Gas diffusion layer design focusing on the structure of the contact face with catalyst layer against water flooding in polymer electrolyte fuel cell

High humidity must be maintained inside polymer electrolyte fuel cells to achieve high ion conductivity. However, water condensation blocks the diffusion of the reaction gas in the gas diffusion layer under water saturation conditions which are produced by the product water. This effect is known as flooding and causes a sudden drop in the cell voltage. Therefore, advanced water management is required in such fuel cells. Internal water management is generally carried out by making adjustments to the gas diffusion layer. This study reports that the extremely highly flood-resistant gas diffusion layer has been developed, based on simple carbon paper. It was experimentally revealed that flooding is controlled by a gas diffusion layer with a smaller pore-structure facing the catalyst layer and it is one of the governing factors for flooding in the gas diffusion layer.     

A two-phase model for studying the role of microporous layer and catalyst layer interface on polymer electrolyte fuel cell performance

In this work, a two-phase, two-dimensional model is developed to investigate the role of interfacial voids at the microporous layer (MPL) and catalyst layer (CL) interface on the polymer electrolyte fuel cell (PEFC) performance. The model incorporates the MPL|CL interfacial region as a separate domain and simulates two-phase transport within the interfacial voids. Different case studies, including the experimentally-measured MPL|CL interface and a perfect contact interface, are conducted. Model simulations indicate that the MPL|CL interfacial morphology has a significant effect on performance, particularly in the high current density region (>1.0 A/cm²). The interfacial voids at the MPL|CL interface are found to retain liquid water during operation and induce mass transport resistance, resulting in nearly a 20% reduction in the limiting current density when compared to perfect interfacial contact. The liquid water saturation retained at the interface and the magnitude of the mass and charge transport resistance induced by the interface are found to be highly dependent upon the geometry and size of the interfacial voids. Finally, simulations indicate that the morphology of the MPL|CL interface affects the location where reactions tend to occur in the CL, and also has a direct impact on the temperature distribution within the cathode.     

Membrane resistance and current distribution measurements under various operating conditions in a polymer electrolyte fuel cell

The ability to make spatially resolved measurements in a fuel cell provides one of the most useful ways in which to monitor and optimise their performance. Localised membrane resistance and current density measurements for a single channel polymer electrolyte fuel cell are presented for a range of operating conditions. The current density distribution results are compared with an analytical model that exhibited generally good agreement across a broad range of operating conditions. However, under conditions of high air flow rate, an increase in current is observed along the channel which is not predicted by the model. Under such circumstances, localised electrochemical impedance measurements show a decrease in membrane resistance along the channel. This phenomenon is attributed to drying of the electrolyte at the start of the channel and is more pronounced with increasing operating temperature.     

Effect of air flow on liquid water transport through a hydrophobic gas diffusion layer of a polymer electrolyte membrane fuel cell

The transport of liquid water through an idealized 2-D reconstructed gas diffusion layer (GDL) of a polymer electrolyte membrane (PEM) fuel cell is computed subject to hydrophobic boundary condition at the fibre–fluid interface. The effect of air flow, as would occur in parallel/serpentine/interdigitated type of flow fields, on the liquid water transport through the GDL, ejection into the channel in the form of water droplets and subsequent removal of the droplets has been simulated. Results show that typically water flow through the fibrous GDL occurs through a fingering and channelling type of mechanism. The presence of cross-flow of air has an effect both on the path created within the GDL and on the ejection of water into the channel in the form of droplets. A faster rate of liquid water evacuation through the GDL (i.e., more frequent ejection of water droplets) as well as less flooding of the void space results from the presence of cross-flow. These results agree qualitatively with experimental observations reported in the literature.     

Monodimensional modeling and experimental study of the dynamic behavior of proton exchange membrane fuel cell stack operating in dead-end mode

The dynamic behavior of a five cells proton exchange membrane fuel cell (PEMFC) stack operating in dead-end mode has been studied at room temperature, both experimentally and by simulation. Its performances in “fresh” and “aged” state have been compared. The cells exhibited two different response times: the first one at about 40 ms, corresponding to the time needed to charge the double-layer capacitance, and the second one at about 15–20 s. The first time response was not affected by the ageing process, despite the decrease of the performances, while the second one was. Our simulations indicated that a high amount of liquid water was present in the stack, even in “fresh” state. This liquid water is at the origin of the performances decrease with ageing, due to its effect on decreasing the actual GDL porosity that in turn cause the starving of the active layer with oxygen. As a consequence, it appears that water management issue in a fuel cell operating in dead-end mode at room temperature mainly consists in avoiding pore flooding instead of providing enough water to maintain membrane conductivity.     

Particle size dependence of CO tolerance of anode PtRu catalysts for polymer electrolyte fuel cells

An anode catalyst for a polymer electrolyte fuel cell must be CO-tolerant, that is, it must have the function of hydrogen oxidation in the presence of CO, because hydrogen fuel gas generated by the steam reforming process of natural gas contains a small amount of CO. In the present study, PtRu/C catalysts were prepared with control of the degree of Pt-Ru alloying and the size of PtRu particles. This control has become possible by a new method of heat treatment at the final step in the preparation of catalysts. The CO tolerances of PtRu/C catalysts with the same degree of Pt-Ru alloying and with different average sizes of PtRu particles were thus compared. Polarization curves were obtained with pure H₂ and CO/H₂ (CO concentrations of 500-2040 ppm). It was found that the CO tolerance of highly dispersed PtRu/C (high dispersion (HD)) with small PtRu particles was much higher than that of poorly dispersed PtRu/C (low dispersion (LD)) with large metal particles. The CO tolerance of PtRu/C (HD) was higher than that of any commercial PtRu/C. The high CO tolerance of PtRu/C (HD) is thought to be due to efficient concerted functions of Pt, Ru, and their alloy.