Three-dimensional non-isothermal model development of high temperature PEM Fuel Cells

A three-dimensional non-isothermal mathematical model is developed in a triple mixed serpentine flow multichannel domain for a high temperature PEM Fuel Cell having a phosphoric acid doped PBI membrane as electrolyte and an active area of 25 cm² within Comsol Multiphysics. The inlet temperatures of cathode and anode reactants are taken as 438 K. Model predicts pressure, and temperature distribution along the channels and membrane current density distribution over the membrane electrodes. The model results are obtained at two different operation voltages, 0.45 V and 0.60 V. Resulting average current densities are respectively 0.313 A cm^?2 and 0.224 A cm^?2. The non-isothermal model results are compared to isothermal model results from a previous study and various other single channel non-isothermal model results available in the literature. The pressure drop at cathode compartment is predicted to be 6500 Pa, whereas it is found to be 6400 Pa for the isothermal model. The temperature difference within the system is found to be 0.18 K for the operation voltage of 0.6 V, whereas this value increases to 0.31 K for the operation voltage of 0.45 V. The temperature difference isocontours are illustrated for the whole cell. Considering changes in temperature, one can employ isothermal operation assumption for this system as an approximation and simplification for the governing equations, since the variation in the temperature within the cell is less than 1 K. It should be emphasized that multichannel model predictions are more realistic compared to single channel models. The model developed here can be extended to larger electrode active area and different multichannel configurations.     

A PEM fuel cell model for cold-start simulations

In this paper, a transient multiphase multi-dimensional PEM fuel cell model has been developed in the mixed-domain framework for elucidating the fundamental physics of fuel cell cold start. Cold-start operations of a PEM fuel cell at a subfreezing boundary temperature of −20 °C under both constant current and constant cell voltage conditions have been numerically examined. Numerical results indicate that the water vapor concentration inside the cathode gas channel affects ice formation in the cathode catalyst layer and thus the cold-start process of the fuel cell. This conclusion demonstrates that high gas flow rates in the cathode gas channel could increase fuel cell cold-start time and benefit the cold-start process. It is shown that the membrane plays a significant role during the cold-start process of a PEM fuel cell by absorbing the product water and becoming hydrated. The time evolutions of ice formation, current density and water content distributions during fuel cell cold-start processes have also been discussed in detail.     

Diagnosis of PEM fuel cell stack dynamic behaviors

In this study, the steady-state performance and dynamic behavior of a commercial 10-cell Proton Exchange Membrane (PEM) fuel cell stack was experimentally investigated using a self-developed PEM fuel cell test stand. The start-up characteristics of the stack to different current loads and dynamic responses after current step-up to an elevated load were investigated. The stack voltage was observed to experience oscillation at air excess coefficient of 2 due to the flooding/recovery cycle of part of the cells. In order to correlate the stack voltage with the pressure drop across the cathode/anode, fast Fourier transform was performed. Dominant frequency of pressure drop signal was obtained to indicate the water behavior in cathode/anode, thereby predicting the stack voltage change. Such relationship between frequency of pressure drop and stack voltage was found and summarized. This provides an innovative approach to utilize frequency of pressure drop signal as a diagnostic tool for PEM fuel cell stack dynamic behaviors.     

Membrane degradation in PEM fuel cells: From experimental results to semi-empirical degradation laws

Chemical membrane degradation is one of the main lifetime-limiting factors for proton exchange membrane fuel cells. In this paper, the degradation of state-of-the-art catalyst coated membranes with an ePTFE reinforcement layers is studied under various operating conditions to quantify the impact of cell potential, pressure and humidity on degradation rate. The membrane electrode assembly has been monitored using various experimental techniques, including electrochemical techniques, post-mortem analyses and fluoride release measurements of exhaust water. Semi-empirical laws are proposed to quantitatively model the observed impact of cell potential and cathode oxygen partial pressure on fluoride release rate and membrane thinning. For the low humidity cases, the observed membrane thinning, the hole formation and the open circuit voltage drop are correctly captured by the proposed model by considering an initial default in the membrane where the membrane degradation, which is highly non-linear, will accelerate. Regarding humidity, a higher value does not reduce the degradation rate but seems to induce a more homogeneous repartition of the degradation preventing the formation of local pinholes and therefore extending the fuel cell lifetime.     

Numerical investigation of transient responses of a PEM fuel cell using a two-phase non-isothermal mixed-domain model

In this paper, a transient two-phase non-isothermal PEM fuel cell model has been developed based on the previously established two-phase mixed-domain approach. This model is capable of solving two-phase flow and heat transfer processes simultaneously and has been applied herein for two-dimensional time-accurate simulations to fully examine the effects of liquid water transport and heat transfer phenomena on the transient responses of a PEM fuel cell undergoing a step change of cell voltage, with and without condensation/evaporation interfaces. The present numerical results show that under isothermal two-phase conditions, the presence of liquid water in the porous materials increases the current density over-shoot and under-shoot, while under the non-isothermal two-phase conditions, the heat transfer process significantly increases the transient response time. The present studies also indicate that proper consideration of the liquid droplet coverage at the GDL/GC interface results in the increased liquid saturation values inside the porous materials and consequently the drastically increased over-shoot and under-shoot of the current density. In fact, the transient characteristics of the interfacial liquid droplet coverage could exert influences on not only the magnitude but also the time of the transient response process.     

Detaching behaviors of catalyst layers applied in PEM fuel cells by off-line accelerated test

The detaching behavior of catalyst layers in membrane electrode assembly (MEA) for PEM fuel cells could affect the lifetime of both catalyst layers and membranes. However, this issue is always neglected. Therefore, the study of detaching behavior of catalyst layer is very conducive to investigate the failure mechanism of fuel cells. The detaching of catalyst layers was simulated by dipping membrane electrode assemblies (MEAs) into H₂O₂ solution with or without Fe²⁺. We observed the presence of detaching of catalyst layers and found the varied detaching behaviors with different accelerated testing solutions: a layered-type detaching behavior is shown for the catalyst layer treated with 30% H₂O₂ solution, whereas a crack-like detaching behavior in the case of 30% H₂O₂ solution with Fe²⁺ species (or Fenton's test). At the same time, the layered-type detaching of catalyst layers has a higher detaching rate than the crack-like detaching. These detaching behaviors should have an inherent link to degradation of recast-ionomer (Nafion) films in catalyst layers. In addition, the effect of detaching behaviors of catalyst layers on the lifetime of fuel cells has been studied by hydrogen crossover measurement, and shows that, for the crack-like detaching, the membrane has a shorter lifetime than that for the layered detaching.     

Cold pre-compression of membrane electrode assembly for PEM fuel cells

Direct compression from the land structure of bipolar plate in a PEM fuel cell is considered as an important factor for the higher performance under the land than under the channel areas. Therefore the objective of this study is to determine if a cold pre-compression treatment on the whole membrane electrode assembly (MEA) area may have a significant positive effect on the overall performance of the cell. Five different levels of cold pre-compression have been applied and the experimental results show that the overall performance of the cell first increases with the level of compression to a maximum, and then decreases. These results clearly show that cold pre-compression of the MEA can significantly enhance the performance of the entire cell and there exists an optimal level of compression. Results of electrochemical impedance spectroscopy (EIS) show that the cold pre-compression results in a significant reduction in charge transfer resistance, especially in the high current density region. Further study by the cyclic voltammetry (CV) shows that the electro-chemical area (ECA) is changed with the different cold pre-compressed MEAs and there exists an optimal compression that results in the maximum ECA.     

Experimental and theoretical analysis of ionomer/carbon ratio effect on PEM fuel cell cold start operation

The effect of ionomer/carbon (I/C) ratio on proton exchange membrane (PEM) fuel cell cold start is investigated experimentally with theoretical water transport analysis. The scanning electron microscope (SEM) images show larger agglomerates and smaller effective reaction area by increasing the I/C ratio from 0.7 to 1.7. For normal operation, increasing the I/C ratio can improve the humidity tolerance, especially in the cathode. For cold start >?10 °C, a lower I/C ratio leads to better performance because the core reaction area is shifted towards the membrane, leading to more membrane water absorption and slower ice formation. For <?15 °C, the total water production is low and almost the same for the different I/C ratios because the ice formation takes place before effective membrane water absorption; and although the cathode catalyst layer (CL) and micro-porous layer (MPL) can provide sufficient space to store all the ice, higher I/C ratios (e.g. 1.2) still cause more ice formation in GDL and flow channel because the core reaction area becomes closer to GDL. The results show that the CL design has significant effect on the cold start performance, and there is a potential for further improvement.     

A two-phase non-isothermal mixed-domain PEM fuel cell model and its application to two-dimensional simulations

In this paper, a two-phase non-isothermal PEM fuel cell model based on the previously developed mixed-domain PEM fuel cell model with a consistent treatment of water transport in MEA has been established using the traditional two-fluid method. This two-phase multi-dimensional PEM fuel cell model could fully incorporate both the anode and cathode sides, properly account for the various water phases, including water vapor, water in the membrane phase, and liquid water, and truly enable numerical investigations of water and thermal management issues with the existence of condensation/evaporation interfaces in a PEM fuel cell. This two-phase model has been applied in this paper in a two-dimensional configuration to determine the appropriate condensation and evaporation rate coefficients and conduct extensive numerical studies concerning the effects of the inlet humidity condition and temperature variation on liquid water distribution with or without a condensation/evaporation interface.     

Electrochemical characterization of sulfonated PEEK-WC membranes for PEM fuel cells

Sulfonated PEEK-WC polymer was obtained according to chloro-sulfonic acid procedure making possible the preparation of different membrane samples with a sulfonation degree from 48 to 90%. Dense membranes were prepared from casting solutions of S-PEEK-WC dissolved in DMF. Proton conductivity measurements were performed on such S-PEEK-WC membranes in a range of temperature from 30 to 120 °C and 100% of relative humidity, reaching 2.5 × 10⁻² S cm⁻¹ as the best value at 100 °C and with a sulfonation degree of 90%. In the meanwhile, the open circuit voltage of this S-PEEK-WC membrane (DS = 90%) varied from 0.963 V at 60 °C to 0.802 V at 100 °C, demonstrating that an increase of temperature negatively affects the membrane performance due to the mechanical properties degradation. In this work, a wide experimental campaign was carried out to investigate the electrochemical performances in terms of polarization curves, open circuit voltage and proton conductivity of S-PEEK-WC membranes as well as the fuel crossover and water uptake.     

Prediction performance of PEM fuel cells by gene expression programming

In the present study, gene expression programming has been utilized to evaluate the output voltage of different PEM fuel cells as the performance symbol of these structures. A total number of 843 data were collected from the literature, randomly divided into 682 and 161 sets, and then trained and tested, respectively by different models. The used data as input parameters were consisted of current density, fuel cell temperature, anode humidification temperature, cathode humidification temperature, operating pressures, fuel cell type, O₂ flow rate, air flow rate and active surface area of the PEM fuel cells. According to these input parameters, in the gene expression programming models, the voltage of each PEM fuel cell in different conditions was predicted. The training and testing results in the gene expression programming model have shown an acceptable potential for predicting voltage values of the PEM fuel cells in the considered range.     

Fast start-up of a diesel fuel processor for PEM fuel cells

Fuel cell systems based on liquid fuels are particularly suitable for auxiliary power generation due to the high energy density of the fuel and its easy storage. Together with industrial partners, Oel-Waerme-Institut is developing a 3 kW_el PEM fuel cell system based on diesel steam reforming to be applied as an APU for caravans and yachts. The start-up time of a fuel cell APU is of crucial importance since a buffer battery has to supply electric power until the system is ready to take over. Therefore, the start-up time directly affects the battery capacity and consequently the system size, weight, and cost.     

Experimental and modelling studies of CO poisoning in PEM fuel cells

This article is an examination of the CO poisoning and cleaning (stripping) phenomenon that occur in a PEM fuel cell operating on an impure hydrogen stream such as reformed hydrocarbons or alcohols. A range of experimental results including cell polarization curves, measurements of spontaneous and transient oscillations of the anode potential and current pulsing behaviour are presented. Detailed examination of the pulsing process has shown that optimization of both the pulse width and pulse initiation potential will have an important impact on the overall fuel cell efficiency. To optimize these processes, the development of a mathematical model to understand and control the poisoning and cleaning processes is going to be important. In this paper, we have extended the model of Zhang et al. [J. Zhang, Investigation of CO tolerance in proton exchange membrane fuel cells, PhD thesis, Worcester Polytechnic Institute, June, 2004; J. Zhang, R. Datta, J. Electrochem. Soc. 149 (2002) A1423; J. Zhang, J.D. Fehribach, R. Datta, J. Electrochem. Soc. 151 (2004) A689] to include mass transfer effects. It is shown that this new model gives results that are in reasonable agreement with our experimental data.     

Simulation of species transport and water management in PEM fuel cells

A single phase computational fuel cells model is presented to elucidate three-dimensional interactions between mass transport and electrochemical kinetics in proton exchange membrane (PEM) fuel cells with straight gas channels. The governing differential equations are solved over a single computational domain, which consists of a gas channel, gas diffusion layer, and catalyst layer for both the anode and cathode sides of the cell as well as the solid polymer membrane. Emphasis is placed on obtaining a basic understanding of how three-dimensional flow and transport phenomena in the air cathode impact the electrochemical process in the flow field. The complete cell model has been validated against experimentally measured polarization curve, showing good accuracy in reproducing cell performance over moderate current density interval. Fully three-dimensional results of the flow structure and species profiles are presented for cathode flow field. The effects of pressure on oxygen transport and water removal are illustrated through main axis of the flow structure. The model results indicate that oxygen concentration in reaction sites is significantly affected by pressure increase which leads to rising fuel cells power.     

1D and 3D numerical simulations in PEM fuel cells

The potential of fuel cells for clean and efficient energy conversion is generally recognized.The proton-exchange membrane (PEM) fuel cells are one of the most promising types of fuel cells. Models play an important role in fuel cell development since they enable the understanding of the influence of different parameters on the cell performance allowing a systematic simulation, design and optimization of fuel cells systems. In the present work, one-dimensional and three-dimensional numerical simulations were performed and compared with experimental data obtained in a PEM fuel cell. The 1D model, coupling heat and mass transfer effects, was previously developed and validated by the same authors [1] and [2]. The 3D numerical simulations were obtained using the commercial code FLUENT - PEMFC module.The results show that 1D and 3D model simulations considering just one phase for the water flow are similar, with a slightly better accordance for the 1D model exhibiting a substantially lower CPU time. However both numerical results over predict the fuel cell performance while the 3D simulations reproduce very well the experimental data. The effect of the relative humidity of gases and operation temperature on fuel cell performance was also studied both through the comparison of the polarization curves for the 1D and 3D simulations and experimental data and through the analysis of relevant physical parameters such as the water membrane content and the proton conductivity. A polarization curve with the 1D model is obtained with a CPU time around 5 min, while the 3D computing time is around 24 h. The results show that the 1D model can be used to predict optimal operating conditions in PEMFCs and the general trends of the impact on fuel cell performance of several important physical parameters (such as those related to the water management). The use of the 3D numerical simulations is indicated if more detailed predictions are needed namely the spatial distribution and visualization of various relevant parameters.An important conclusion of this work is the demonstration that a simpler model using low CPU has potential to be used in real-time PEMFC simulations.     

Thermal analysis of air-cooled PEM fuel cells

Air-cooled proton exchange membrane fuel cells (PEMFCs), having combined air cooling and oxidant supply channels, offer significantly reduced bill of materials and system complexity compared to conventional, water-cooled fuel cells. Thermal management of air-cooled fuel cells is however a major challenge. In the present study, a 3D numerical thermal model is presented to analyze the heat transfer and predict the temperature distribution in air-cooled PEMFCs. Conservation equations of mass, momentum, species, and energy are solved in the oxidant channel, while energy equation is solved in the entire domain, including the membrane electrode assembly (MEA) and bipolar plates. The model is validated with experiments and can reasonably predict the maximum temperature and main temperature gradients in the stack. Large temperature variations are found between the cool incoming air flow and the hot bipolar plates and MEA, and in contrast to water-cooled fuel cells, significant temperature gradients are detected in the flow direction. Furthermore, the air velocity and in-plane thermal conductivity of the plate are found to play an important role in the thermal performance of the stack.     

Numerical studies of liquid water behaviors in PEM fuel cell cathode considering transport across different porous layers

In this paper, a two-phase two-dimensional PEM fuel cell model, which is capable of handling liquid water transport across different porous materials, is employed for parametric studies of liquid water transport and distribution in the cathode of a PEM fuel cell. Attention is paid particularly to the coupled effects of two-phase flow and heat transfer phenomena. The effects of key operation parameters, including the outside cell boundary temperature, the cathode gas humidification condition, and the cell operation current, on the liquid water behaviors and cell performance have been examined in detail. Numerical results elucidate that increasing the fuel cell temperature would not only enhance liquid water evaporation and thus decrease the liquid saturation inside the PEM fuel cell cathode, but also change the location where liquid water is condensed or evaporated. At a cell boundary temperature of 80 °C, liquid water inside the catalyst layer and gas diffusion media under the current-collecting land would flow laterally towards the gas channel and become evaporated along an interface separating the land and channel. As the cell boundary temperature increases, the maximum current density inside the membrane would shift laterally towards the current-collecting land, a phenomenon dictated by membrane hydration. Increasing the gas humidification condition in the cathode gas channel and/or increasing the operating current of the fuel cell could offset the temperature effect on liquid water transport and distribution.     

Numerical evaluation of a PEM fuel cell with conventional flow fields adapted to tubular plates

In this research a 3D numerical study on a PEM fuel cell model with tubular plates is presented. The study is focused on the performance evaluation of three flow fields with cylindrical geometry (serpentine, interdigitated and straight channels) in a fuel cell. These designs are proposed not only with the aim to reduce the pressure losses that conventional designs exhibit with rectangular flow fields but also to improve the mass transport processes that take place in the fuel cell cathode. A commercial computational fluid dynamics (CFD) code was used to solve the numerical model. From the numerical solution of the fluid mechanics equations and the electrochemical model of Butler-Volmer different analysis of pressure losses, species concentration, current density, temperature and ionic conductivity were carried out. The results were obtained at the flow channels and the catalyst layers as well as in the gas diffusion layers and the membrane interfaces. Numerical results showed that cylindrical channel configurations reduced the pressure losses in the cell due to the gradual reduction of the angle at the flow path and the twist of the channel, thus facilitating the expulsion of liquid water from the gas diffusion layers and in turn promoting a high oxygen concentration at the triple phase boundary of the catalyst layers. Moreover, numerical results were compared to polarization curves and the literature data reported for similar designs. These results demonstrated that conventional flow field designs applied to conventional tubular plates have some advantages over the rectangular designs, such as uniform pressure and current density distributions among others, therefore they could be considered for fuel cell designs in portable applications.     

Parametric sensitivity analysis of PEM fuel cell electrochemical Model

In order to obtain an adequate PEM Fuel Cell model, it is necessary to define the values for a specific group of modeling parameters. The disagreements between the experimental and simulation results arise because of uncertainties stemming not only from the experimental measurements, but also from the modeling parameters used in the theoretical calculations. The modeling parameters were analyzed using Multi-Parametric Sensitivity Analysis (MPSA). This paper presents a sensitivity investigation of PEMFC electrochemical models and aims to determine the relative importance of each parameter on the modeling results. A computer program is written in Dev-cpp environment to calculate the sensitivity index for each parameter. As a result, the parameters were classified according to their influence in the modeling results as: insensitive, sensitive and highly sensitive. Thus it is possible to evaluate the relative importance of each parameter to the simulation accuracy. The present work benefits to understand the most effecting parameters, thus it helps the manufacturer to be more cautious in defining the exact value for them.     

On the influence of methanol addition on the performances of PEM fuel cells operated at subzero temperatures

The storage and the operation of proton exchange membrane fuel cells (PEM FCs) at subzero temperatures result in the ageing and degradation of membrane-electrode assemblies (MEAs). In this study, we investigated the effect of a freeze-thaw temperature cycles (from ambient down to ?80 °C) on various properties of PFSA membranes and on the performance level of MEAs. The beneficial effects resulting from the addition of methanol vapor to the hydrogen have been put into evidence. Small angle x-ray scattering (SAXS) data have been measured on membranes swollen with water and water-methanol mixtures, to identify possible microstructure differences. It was found that the addition of methanol tends to increase the ionic resistivity of the membranes but has a protective effect on the catalytic layers during the freeze-thaw cycles. The degradation rate of the catalytic layer was reduced by almost a factor of two as a result of optimal methanol addition.