Numerical analysis of gas crossover effects in polymer electrolyte fuel cells (PEFCs)

The gas crossover phenomenon in polymer electrolyte fuel cells (PEFCs) is an indicator of membrane degradation. The objective of this paper is to numerically investigate the effects of hydrogen and oxygen crossover through the membrane in PEFCs. A gas crossover model is newly developed and implemented in a comprehensive multi-dimensional, multi-phase PEFC model developed earlier. A parametric study is carried out to investigate the effects of the crossover diffusion coefficients for hydrogen and oxygen as well as the membrane thickness. The simulation results demonstrate that the hydrogen crossover induces an additional oxygen reduction reaction (ORR) and consequently causes an additional voltage drop, while the influence of oxygen crossover on PEFC performance is relatively insignificant because it leads to the hydrogen/oxygen chemical reaction at the anode side. Finally, using the time-dependent gas crossover data that are available in the literature (measured in days), we conduct gas crossover simulations to examine the effects of increased gas crossover due to membrane degradation on PEFC performance and successfully demonstrate decaying polarization curves with respect to time. This study clearly elucidates the detailed mechanisms of the hydrogen and oxygen crossover phenomena and their effect on PEFC performance and durability.     

Numerical analysis of effects of gas crossover through membrane pinholes in high-temperature proton exchange membrane fuel cells

Durability is a major issue in the widespread commercialization of proton exchange membrane fuel cells (PEMFCs). Various failure modes have been identified over their long runtime. These mainly originate from membrane and catalyst layer failures. One of the most common failure modes in PEMFCs is due to pinhole formation in the membrane and resultant reactant gas crossover through the membrane. Gas crossover induces several critical problems in PEMFCs, including severe reactant depletion in the downstream regions, mixed potential at the electrodes, and formation of local hot spots by hydrogen/oxygen catalytic reaction, which indicates that the cell performance decreases with increasing gas crossover. In this study, we numerically investigate the effects of gas crossover on the performance of a high-temperature PEMFC based on a phosphoric-acid-doped polybenzimidazole (PBI) membrane. In contrast to previous gas-crossover studies 1 and 2 in which uniform gas crossover throughout the entire membrane has been simply assumed, our focus is on examining the impacts of localized gas crossover due to membrane pinholes. Numerical simulations are carried out via arbitrarily assuming pinholes in the membrane. The simulation results clearly show that the presence of pinholes in the membrane significantly disrupts the species, current density, and temperature distributions. Our findings may improve the fundamental and detailed understanding of localized gas-crossover phenomena through the membrane pinholes and the influence of these phenomena on high-temperature PEMFC operation.     

Research on two‐phase flow considering hydrogen crossover in the membrane for a polymer electrolyte membrane fuel cell

Hydrogen crossover has an important effect on the performance and durability of the polymer electrolyte membrane fuel cell (PEMFC). Severe hydrogen crossover can accelerate the degradation of membrane and thus increase the possibility of explosion. In this study, a two‐phase, two‐dimensional, and multiphysics field coupling model considering hydrogen crossover in the membrane for PEMFC is developed. The model describes the distributions of reactant gases, current density, water content in membrane, and liquid water saturation in cathode electrodes of PEMFC with intrinsic hydrogen permeability, which is usually neglected in most PEMFC models. The conversion processes of water between gas phase, liquid phase, and dissolved water in PEMFC are simulated. The effects of changes in hydrogen permeability on PEMFC output performance and distributions of reactant gases and water saturation are analyzed. Results showed that hydrogen permeability has a marked effect on PEMFC operating under low current density conditions, especially on the open circuit voltage (OCV) with the increase of hydrogen permeability. On the contrary, the effect of hydrogen permeability on PEMFC at high current density is negligible within the variation range of hydrogen permeability in this study. The nonlinear relations of OCV with hydrogen diffusion rate are regressed.     

In-situ experimental characterization of the clamping pressure effects on low temperature polymer electrolyte membrane electrolysis

The recent acceleration in hydrogen production's R&D will lead the energy transition. Low temperature polymer electrolyte membrane electrolysis (LT-PEME) is one of the most promising candidate technologies to produce hydrogen from renewable energy sources, and for synthetic fuel production. LT-PEME splits water into hydrogen and oxygen when the voltage is applied between anode and cathode. Electrical current forces the positively charged ions to migrate to negatively charged cathode through PEM, where hydrogen is produced. Meanwhile, oxygen is produced at the anode side electrode and escapes as a gas with the circulating water.The effects of clamping pressure (P_c) on the LT-PEME cell performance, polarization resistances, and hydrogen and water crossover through the membrane, and hydrogen and oxygen production rate are studied. A 50 cm² active area LT-PEME cell designed and manufactured in house is utilized in this work.Higher P_c has shown higher cell performance this refers to lower ohmic and activation resistances. Water crossover from anode to cathode is slightly decreased at higher P_c resulting in a slight decrease in hydrogen crossover from cathode to anode. Also, the percentage of hydrogen in the produced oxygen at the anode side is significantly reduced at higher P_c and at lower current density.     

Effect of cooling surface temperature difference on the performance of high-temperature PEMFCs

Internal temperature distribution of the high-temperature proton exchange membrane fuel cell (HT-PEMFC) is affected by the cooling temperature, heat generation and reactant gas flow. Reasonable temperature control is helpful to improve the fuel cell performance and durability. In this work, a three-dimensional model that couples the reactant flows, species transport, heat transfer, charge transfer, and electrochemical reaction, was developed to simulate the HT-PEMFC operation. A solid mechanics model was established to analyze the stress distribution of the fuel cell. The polarization curves, distributions of temperature, membrane proton conductivity, current density and stress are investigated for different cooling surface temperature. Furthermore, the effect of assembly temperature on the stress of phosphoric acid-doped polybenzimidazole (PBI) membrane is discussed. Results reveals that the peak power density and uniformity of current density decrease with the increase of cooling surface temperature difference. The peak power density decreases by 9.14% when the temperature difference increases from 0 K to 40 K. The cooling surface temperature difference of less than 10 K and the voltage range in 0.5–0.7 V can achieve better current density uniformity and smaller current density change rate. In addition, the membrane in fuel cell has the highest stress, and increasing the assembly temperature is helpful to reduce the membrane stress. When the assembly temperature increases from 293.15 K to 343.15 K, the max and min compressive stresses in membrane in-plane decrease from 39.436 MPa to 31.416 MPa–24.934 MPa and 17.369 MPa at the temperature difference of 30 K, which decreases by 36.77% and 44.7%, respectively.     

Novel technique for measuring oxygen crossover through the membrane in polymer electrolyte membrane fuel cells

In this study, the exact amount of oxygen crossover that reacts with hydrogen has been investigated using a mass spectrometer system. By measuring the amount of oxygen crossover that reacts with hydrogen, the exact amount of oxygen crossover that affects membrane degradation and/or water generation can be calculated under the fuel cell operating conditions. The amount of oxygen crossover that reacts with hydrogen is expressed as an effective oxygen crossover ratio, which is in a range between 0.927 and 0.933 under the fuel cell operating temperature conditions. This means that approximately 93% of the entire oxygen crossover through the membrane can affect membrane degradation and/or water generation at the anode catalyst layer. Thus, the effective oxygen crossover ratio should be considered as a novel index of oxygen crossover because it represents the exact amount of oxygen crossover that reacts with hydrogen.     

In situ measurements of water crossover through the membrane for direct methanol fuel cells

We show analytically that the water-crossover flux through the membrane used for direct methanol fuel cells (DMFCs) can be in situ determined by measuring the water flow rate at the exit of the cathode flow field. This measurement method enables investigating the effects of various design and geometric parameters as well as operating conditions, such as properties of cathode gas diffusion layer (GDL), membrane thickness, cell current density, cell temperature, methanol solution concentration, oxygen flow rate, etc., on water crossover through the membrane in situ in a DMFC. Water crossover through the membrane is generally due to electro-osmotic drag, diffusion and back convection. The experimental data showed that diffusion dominated the total water-crossover flux at low current densities due to the high water concentration difference across the membrane. With the increase in current density, the water flux by diffusion decreased, but the flux by back convection increased. The corresponding net water-transport coefficient was also found to decrease with current density. The experimental results also showed that the use of a hydrophobic cathode GDL with a hydrophobic MPL could substantially reduce water crossover through the membrane, and thereby significantly increasing the limiting current as the result of the improved oxygen transport. It was found that the cell operating temperature, oxygen flow rate and membrane thickness all had significant influences on water crossover, but the influence of methanol concentration was negligibly small.     

Water management in a passive direct methanol fuel cell

Passive direct methanol fuel cells (DMFCs) are under development for use in portable applications because of their enhanced energy density in comparison with other fuel cell types. The most significant obstacles for DMFC development are methanol and water crossover because methanol diffuses through the membrane generating heat but no power. The presence of a large amount of water floods the cathode and reduces cell performance. The present study was carried out to understand the performance of passive DMFCs, focused on the water crossover through the membrane from the anode to the cathode side. The water crossover behaviour in passive DMFCs was studied analytically with the results of a developed model for passive DMFCs. The model was validated with an in‐house designed passive DMFC. The effect of methanol concentration, membrane thickness, gas diffusion layer material and thickness and catalyst loading on fuel cell performance and water crossover is presented. Water crossover was lowered with reduction on methanol concentration, reduction of membrane thickness and increase on anode diffusion layer thickness and anode and cathode catalyst layer thickness. It was found that these conditions also reduced methanol crossover rate. A membrane electrode assembly was proposed to achieve low methanol and water crossover and high power density, operating at high methanol concentrations. The results presented provide very useful and actual information for future passive DMFC systems using high concentration or pure methanol. Copyright © 2012 John Wiley & Sons, Ltd.     

Experimental investigation of CO tolerance in high temperature PEM fuel cells

In the present work, the effect of operating a high temperature proton exchange membrane fuel cell (HT-PEMFC) with different reactant gases has been investigated throughout performance tests. Also, the effects of temperature on the performance of a HT-PEMFC were analyzed at varying temperatures, ranging from 140 °C to 200 °C. Increasing the operating temperature of the cell increases the performance of the HT-PEMFC. The optimum operating temperature was determined to be 160 °C due to the deformations occurring in the cell components at high working temperatures. To investigate the effects of CO on the performance of HT-PEMFC, the CO concentration ranged from 1 to 5 vol %. The current density at 0.6 V decreases from 0.33 A/cm² for H₂ to 0.31 A/cm² for H₂ containing 1 vol % CO, to 0.29 A/cm² for 3 vol % CO, and 0.25 A/cm² for 5 vol % CO, respectively. The experimental results show that the presence of 25 vol % CO₂ or N₂ has only a dilution effect and therefore, there is a minor impact on the HT-PEMFC performance. However, the addition of CO to H₂/N₂ or H₂/CO₂ mixtures increased the performance loss. After long-term performance test for 500 h, the observed voltage drop at constant current density was obtained as ～14.8% for H₂/CO₂/CO (75/22/3) mixture. The overall results suggest that the anode side gas mixture with up to 5 vol % CO can be supplied to the HT-PEMFC stack directly from the reformer.     

An analytical model for hydrogen and nitrogen crossover rates in proton exchange membrane fuel cells

In this paper, the hydrogen and nitrogen crossover through the membrane in proton exchange membrane fuel cells, are investigated by developing a semi-empirical analytical model. Different factors that affect the gas crossover rates were considered including pressure drop in gas diffusion layer (GDL) and catalyst layer (CL), operating temperature, relative humidity (RH) of the reactants, GDL compression, and the current density effect on the membrane temperature. The model is validated by published experimental data. It is found that RH is the most important parameter, followed by temperature. The hydrogen pressure drop through GDL and CL greatly depends on the GDL substrate properties, microporous layer (MPL) and CL. When permeability is low, an increase in current density reduces gas crossover. GDL compression, when MPL is used, was found to have a low impact on gas crossover. Gas crossover is improved with current density due to an increase in membrane temperature.     

Optimal operating parameters for advanced alkaline water electrolysis

Advanced zero-gap alkaline electrolyzers can be operated at a significantly higher current density than traditional alkaline electrolyzers. We have investigated how their performance is influenced by diaphragm thickness, temperature and pressure. For this a semi-empirical current-voltage model has been developed based on experimental data of a 20 Nm³/h electrolyzer. The model was extrapolated to thinner diaphragm thicknesses and higher temperatures showing that a nominal current density of 1.8 A cm^?2 is possible with a 0.1 mm diaphragm at 100 °C. However, these operating parameters also lead to increased gas crossover, which limits the ability to operate at low loads. A gas crossover model has been developed, which shows that crossover is mainly driven by diffusive transport of hydrogen, caused by a high local supersaturation at the diaphragm surface. To enable a low minimum load of 10% the operating pressure should be kept below 8 bara.     

Effects of inlet relative humidity (RH) on the performance of a high temperature-proton exchange membrane fuel cell (HT-PEMFC)

A high temperature-proton exchange membrane fuel cells (HT-PEMFC) based on phosphoric acid (PA)-doped polybenzimidazole (PBI) membrane is able to operate at elevated temperature ranging from 100 to 200 °C. Therefore, it is evident that the relative humidity (RH) of gases within a HT-PEMFC must be minimal owing to its high operating temperature range. However, it has been continuously reported in the literature that a HT-PEMFC performs better under higher inlet RH conditions. In this study, inlet RH dependence on the performance of a HT-PEMFC is precisely studied by numerical HT-PEMFC simulations. Assuming phase equilibrium between membrane and gas phases, we newly develop a membrane water transport model for HT-PEMFCs and incorporate it into a three-dimensional (3-D) HT-PEMFC model developed in our previous study. The water diffusion coefficient in the membrane is considered as an adjustable parameter to fit the experimental water transport data. In addition, the expression of proton conductivity for PA-doped PBI membranes given in the literature is modified to be suitable for commercial PBI membranes with high PA doping levels such as those used in Celtec^® MEAs. Although the comparison between simulations and experiments shows a lack of agreement quantitatively, the model successfully captures the experimental trends, showing quantitative influence of inlet RH on membrane water flux, ohmic resistance, and cell performance during various HT-PEMFC operations.     

Numerical study of high temperature proton exchange membrane fuel cell (HT-PEMFC) with a focus on rib design

The rib size is a critical engineering design parameter for high temperature proton exchange membrane fuel cell (HT-PEMFC) stack development, yet it hasn't been studied for HT-PEMFC. A three-dimensional, non-isothermal model was developed in this work to investigate the effect of channel to rib width ratios (CRWR) on the performance of HT-PEMFC. The reaction heat caused by entropy change was divided into cathodic half-reaction heat and anodic half-reaction heat. The results show that the ratio value significantly influence the gas diffusion, electron conduction and the distribution of current density in the porous electrodes. Increasing this ratio facilitates gas transport in the porous electrode but causes higher ohmic loss due to longer distance for electron conduction. As a result, an optimal ratio of about 1 is observed, which results in a peak power density of 0.428 W/cm². High current density is observed under the channel with a small ratio value while a high ratio value would cause high current density to appear under the rib, signifying the rib size effect on electrochemical behavior of HT-PEMFC. Apart from the electrical power output, the CRWR value also greatly influences the fluid flow and temperature distribution inside the cell, which would influence the long-term stability of HT-PEMFC. In the subsequent studies, efforts will be made to develop new stack configurations with more uniform gas distribution, short electron conduction path and low temperature gradient.     

Optimization of graded catalyst layer to enhance uniformity of current density and performance of high temperature-polymer electrolyte membrane fuel cell

The optimal use of catalyst materials is essential to improve the performance, durability and reduce the overall cost of the fuel cell. The present study is related to spatial distributions of current and overpotential for various graded catalyst structures in a high temperature-polymer electrolyte membrane fuel cell (HT-PEMFC). The effect of catalyst gradient across the catalytic layer (CL) thickness and along the channel and their combination on cell performance and catalyst utilization is investigated. The graded catalytic structure comprises two, three, or multiple layers of catalyst distribution. For a total cathode catalyst loading of 0.35 mg/cm², higher loading near the membrane presents improved cell performance and catalyst utilization due to reduced limitations caused by oxygen and ion diffusions. However, non-uniformity in the current distribution is significantly increased. The increase in the catalyst loading along the reactant flow provides a substantially uniform current density but lower cell performance. The synergy of varying catalytic profiles across the CL thickness and along the cathode flow direction is investigated. The results emphasize the importance of a rational design of cathode structure and mathematical functions as a strategic tool for functional grading of a CL towards improved uniform current distribution and catalyst utilization.     

Comprehensive one-dimensional,semi-analytical,mathematical model for liquid-feed polymer electrolyte membrane direct methanol fuel cells

Polymer electrolyte membrane direct methanol fuel cells (PEM-DMFCs) have several advantages over hydrogen-fuelled PEM fuel cells; but sluggish methanol electrochemical oxidation and methanol crossover from the anode to the cathode through the PEM are two major problems with these cells. In the present work, a comprehensive one-dimensional, single phase, isothermal mathematical model is developed for a liquid-feed PEM-DMFC, taking into account all the necessary mass transport and electrochemical phenomena. Diffusion and convective effects are considered for methanol transport on the anode side and in the PEM, whereas only diffusional transport of species is considered on the cathode side. A multi-step reaction mechanism is used to describe the electrochemical oxidation of methanol at the anode. Stefan–Maxwell equations are used to describe multi-component diffusion on the cathode side and Tafel type of kinetics is used to describe the simultaneous methanol oxidation and oxygen reduction reactions at the cathode. The model fully accounts for the mixed potential effect caused by methanol crossover at the cathode. It shows excellent agreement with literature data of the limiting current density for different low methanol feed concentrations at different operating temperatures. At high methanol feed concentrations, oxygen depletion on the cathode side, due to excessive methanol crossover, results in mass-transport limitations. The model can be used to optimize the geometric and physical parameters with a view to extracting the highest current density while still keeping a tolerably low methanol crossover.     

Three-dimensional numerical analysis of PEM fuel cells with straight and wave-like gas flow fields channels

Using a three-dimensional computational model, numerical simulations are performed to investigate the performance characteristics of proton exchange membrane fuel cells (PEMFCs) incorporating either a conventional straight gas flow channel or a novel wave-like channel. The simulations focus particularly on the effect of the wave-like surface on the gas flow characteristics, the temperature distribution, the electrochemical reaction efficiency and the electrical performance of the PEMFCs at operating temperatures ranging from 323 K to 343 K. The numerical results reveal that the wave-like surface enhances the transport of the reactant gases through the porous layer, improves the convective heat transfer effect, increases the gas flow velocity, and yields a more uniform temperature distribution. As a result, the efficiency of the catalytic reaction is significantly improved. Consequently, compared to a conventional PEMFC, the PEMFC with a wave-like channel yields a notably higher output voltage and power density.     

Coupled mechanical stress and multi-dimensional CFD analysis for high temperature proton exchange membrane fuel cells (HT-PEMFCs)

We use a combined finite element method (FEM)/computational fluid dynamics (CFD) methodology to numerically investigate the effects of gas diffusion layer (GDL) compression/intrusion on the performance of a phosphoric acid-doped polybenzimidazole (PBI) membrane-based high temperature proton exchange membrane fuel cell (HT-PEMFC). Three-dimensional (3-D) FEM simulations are conducted under various displacement clamping conditions to analyze cell deformation characteristics. Then, a multi-dimensional HT-PEMFC CFD model is applied to the deformed cell geometries to study transport and electrochemical processes during HT-PEMFC operations. Our numerical simulation results reveal that the maximum stresses in the deformed GDLs always occur near the edge of the ribs. The combined effects of GDL compression/intrusion considerably increase spatial non-uniformity in the species and current density distributions, and reduce cell performance.     

Studies on the kinetics of catalytic combustion of deuterium using 0.5% platinum loaded on Dixon ring catalyst

When hydrogen isotopes are present in stoichiometric ratio of 2:1 with oxygen in inert gas such as helium, catalytic combustion is the most promising option to reduce the concentration of hydrogen isotopes and to minimize the associated safety hazards. This is the case, when deuterium and oxygen is formed during radiolysis of heavy water in moderator circuit of Pressurized Heavy Water Reactors (PHWR) and mixed with helium in the cover gas system. In order to design the catalytic reactor for recombination of deuterium and oxygen, the data on catalytic combustion kinetics under the similar process conditions are essential. However, the catalytic combustion data is generally reported for combustion of hydrogen in air, where oxygen is available in excess. The studies on the kinetics of catalytic combustion of deuterium where oxygen is present in stoichiometric ratio of 2:1 in an inert gas medium such as helium, is very scarce. In the present study, the multi-step reaction mechanism of catalytic combustion of hydrogen in presence of platinum catalyst is analyzed for the present process conditions. Based on the analysis, a simple rate expression is proposed for the present process conditions of catalytic combustion of deuterium. Further, 0.5% platinum catalyst is prepared on a stainless steel Dixon ring support with an objective to achieve better heat transfer characteristics and lesser reduction in the catalytic activity due to water adsorption. The kinetic data is generated using a differential packed bed reactor operating in a closed loop. The experiments were conducted at different temperatures using a stoichiometric mixture of deuterium and oxygen in helium. The rate constant for the above proposed model is estimated based on the experimental data at different temperatures. Further, the activation energy and frequency factor are determined and the activation energy for the present catalyst is found to be on the lower side in comparison to literature data.     

Performance analysis of HT-PEFC stacks

The performance analysis of a five-cell HT-PEFC stack is presented. The stack was operated either with pure hydrogen or synthetic reformate on the anode side and air on the cathode side. The overall electric performance and the heat management were analyzed. The local performance was assessed by current density and temperature distribution measurements. For this purpose, a tailor-made measuring board was integrated into the stack assembly. It is shown how the choice of fuel gas composition, reactant stoichiometry, flow direction and cooling affect the current density and temperature distribution.     

Modeling and analysis of a 5 kWe HT-PEMFC system for residential heat and power generation

We present a high-temperature proton exchange membrane fuel cell (HT-PEMFC) system model that accounts for fuel reforming, HT-PEMFC stack, and heat-recovery modules along with heat exchangers and balance of plant (BOP) components. In the model developed for analysis, the reaction kinetics for the fuel reforming processes are considered to accurately capture exhaust gas compositions and reactor temperatures under various operating conditions. The HT-PEMFC stack model is simplified from the three-dimensional HT-PEMFC CFD models developed in our previous studies. In addition, the parasitic power consumption and waste heat release from the various BOP components are calculated based on their heat-capacity curves. An experimental fuel reforming reactor for a 5.0 kW_e HT-PEMFC system was tested to experimentally validate the fuel reforming sub model. The model predictions were found to be in good agreement with the experimental data in terms of exhaust gas compositions and bed temperatures. Additionally, the simulation revealed the impacts of the burner air-fuel ratio (AFR) and the steam reforming reactor steam-carbon ratio on the system performance and efficiency. In particular, the combined heat and power efficiency of the system increased up to 78% when the burner AFR was properly adjusted. This study clearly illustrates that an HT-PEMFC system requires a high degree of thermal integration and optimization of the system configuration and operating conditions.