Numerical modeling and investigation of gas crossover effects in high temperature proton exchange membrane (PEM) fuel cells

A gas crossover model is developed for a high temperature proton exchange membrane fuel cell (HT-PEMFC) with a phosphoric acid-doped polybenzimidazole membrane. The model considers dissolution of reactants into electrolyte phase in the catalyst layers and subsequent crossover of reactant gases through the membrane. Furthermore, the model accounts for a mixed potential on the cathode side resulting from hydrogen crossover and hydrogen/oxygen catalytic combustion on the anode side due to oxygen crossover, which were overlooked in the HT-PEMFC modeling works in the literature. Numerical simulations are carried out to investigate the effects of gas crossover on HT-PEMFC performance by varying three critical parameters, i.e. operating current density, operating temperature and gas crossover diffusivity to approximate the membrane degradation. The numerical results indicate that the effect of gas crossover on HT-PEMFC performance is insignificant in a fresh membrane. However, as the membrane is degraded and hence gas crossover diffusivities are raised, the model predicts non-uniform reactant and current density distributions as well as lower cell performance. In addition, the thermal analysis demonstrates that the amount of heat generated due to hydrogen/oxygen catalytic combustion is not appreciable compared to total waste heat released during HT-PEMFC operations.     

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.     

Comparison of current distributions in proton exchange membrane fuel cells with interdigitated and serpentine flow fields

Current distributions in a proton exchange membrane fuel cell (PEMFC) with interdigitated and serpentine flow fields under various operating conditions are measured and compared. The measurement results show that current distributions in PEMFC with interdigitated flow fields are more uniform than those observed in PEMFC with serpentine flow fields at low reactant gas flow rates. Current distributions in PEMFC with interdigitated flow fields are rather uniform under any operating conditions, even with very low gas flow rates, dry gas feeding or over-humidification of reactant gases. Measurement results also show that current distributions for both interdigitated and serpentine flow fields are significantly affected by reactant gas humidification, but their characteristics are different under various humidification conditions, and the results show that interdigitated flow fields have stronger water removal capability than serpentine flow fields. The optimum reactant gas humidification temperature for interdigitated flow fields is higher than that for serpentine flow fields. The performance for interdigitated flow fields is better with over-humidification of reactant gases but it is lower when air is dry or insufficiently humidified than that for serpentine flow fields.     

Characterization of nitrogen gas crossover through the membrane in proton-exchange membrane fuel cells

Gas crossover phenomenon through a membrane is inevitable in a proton-exchange membrane fuel cell (PEMFC). For nitrogen, the concentration at the cathode side is usually higher than that at the anode side, so N₂ permeates to the anode side. Nitrogen gas crossover (NGC) may cause fuel starvation, if N₂ gas accumulates in the hydrogen recirculation loop. Thus, it is important to determine the NGC under various PEMFC operating conditions. In this study, characterization of NGC under both open circuit voltage (OCV) and power generation conditions is investigated using a mass spectrometer. Under OCV conditions with the PEMFC membrane fully hydrated, N₂ concentration in the anode exit stream increases as cell temperature increases. Nitrogen permeability coefficients (NPC) are calculated based on the obtained N₂ concentration data. The results show that NPC exhibits an Arrhenius type relationship. Under OCV conditions, the maximum NPC is 5.14 × 10^?13 mol m^?1 s^?1 Pa^?1 with an N₂ activation energy of 19.83 kJ. Under power generation conditions, the NGC increases with increasing current density, which is the result of elevated membrane temperature and increased water content. When the anode stoichiometric ratio (SR_A) is lowered, the N₂ concentration increases under all tested current densities. A low hydrogen flow rate, along with a low SR_A at low current density, significantly increases N₂ concentration at the anode outlet.     

Numerical simulation of thermal–hydraulic characteristics in a proton exchange membrane fuel cell

The thermal–hydraulic characteristics of a proton exchange membrane fuel cell (PEMFC) are numerically simulated by a simplified two‐phase, multi‐component flow model. This model consists of continuity, momentum, energy and concentration equations, and appropriate equations to consider the varying flow properties of the gas–liquid two‐phase region in a PEMFC. This gas–liquid two‐phase characteristic is not considered in most of the previous simulation works. The calculated thermal–hydraulic phenomena of a PEMFC are reasonably presented in this paper, which include the distributions of flow vector, temperature, oxygen concentration, liquid water saturation, and current density, etc. Coupled with the electrochemical reaction equations, current flow model can predict the cell voltage vs current density curves (i.e. performance curves), which are validated by the single‐cell tests. The predicted performance curves for a PEMFC agree well with the experimental data. In addition, the positive effect of temperature on the cell performance is also precisely captured by this model. The model presented herein is essentially developed from the thermal–hydraulic point of view and can be considered as a stepping‐stone towards a full complete PEMFC simulation model that can help the optima design for the PEMFC and the enhancement of cell efficiency. Copyright © 2003 John Wiley & Sons, Ltd.     

Influence of anisotropic gas diffusion layers on transport phenomena in a proton exchange membrane fuel cell

The gas diffusion layer is an anisotropic porous medium, which provides pathways for the reactant gases and produced water, conducts the electrical current, removes the generated heat, and provides mechanical support. However, the gas diffusion layer is mostly considered as isotropic in numerical simulations. In the present study, a three‐dimensional, two‐phase flow, and non‐isothermal agglomerate model with consideration of anisotropic permeability, mass diffusivity, thermal conductivity, and electrical conductivity was developed and employed to investigate effects of anisotropic properties on the transport phenomena in a proton exchange membrane fuel cell. The temperature of the anisotropic case is less than that of the isotropic case, and the temperature difference increases with increasing current density. Furthermore, the distributions of the oxygen mass fraction, liquid water saturation, water content, and local current density for both cases are also compared and discussed in detail. The cell performance is over‐predicted by the isotropic model, and the current density of the isotropic case is greater than that of the anisotropic case by approximately 10% at an operating cell voltage of 0.3 V. Both the local transport characteristics and overall cell performance are different for the isotropic and anisotropic cases. Accordingly, it is concluded that the anisotropic properties of the gas diffusion layer must be taken into account in the mathematical model. Copyright © 2017 John Wiley & Sons, Ltd.     

Two-phase flow in GDL and reactant channels of a proton exchange membrane fuel cell

Understanding the effect of two-phase flow in the components of proton exchange membrane fuel cells (PEMFCs) is crucial to water management and subsequently to their performance. The local water saturation in the gas diffusion layer (GDL) and reactant channels influences the hydration of the membrane which has a direct effect on the PEMFC performance. Mass transport resistance includes contributions from both the GDL and reactant channels, as well as the interface between the aforementioned components. Droplet–channel wall interaction, water area coverage ratio on the GDL, oxygen transport resistance at the GDL–channel interface, and two-phase pressure drop in the channels are interlinked. This study explores each factor individually and presents a comprehensive perspective on our current understanding of the two-phase transport characteristics in the PEMFC reactant channels.     

质子交换膜燃料电池内部传热传质三维模拟

针对常规流场质子交换膜燃料电池提出了三维非等温数学模型。模型考虑了电化学反应动力学以及反应气体在流道和多孔介质内的流动和传递过程,详细研究了水在质子膜内的电渗和扩散作用。计算结果表明,反应气体传质的限制和质子膜内的水含量直接决定了电极局部电流密度的分布和电池输出性能;在电流密度大于0.3~0.4A/cm2时开始出现水从阳极到阴极侧的净迁移;高电流密度时膜厚度方向存在很大的温度梯度,这对膜内传递过程有较大影响。     

Optimization of blocked flow field performance of proton exchange membrane fuel cell with auxiliary channels

The flow field optimization design is one of the important methods to improve the performance of proton exchange membrane fuel cell (PEMFC). In this study, a new structure with staggered blocks on the parallel flow channels of PEMFC and auxiliary flow channels under the ribs is proposed. Through numerical calculation method, the effect of blocks auxiliary flow field (BAFF) on pressure drop, reactant distribution and liquid water removal in the fuel cells are investigated. The results show that when the operating voltage is 0.5 V, the current density of BAFF is 21.74% higher than that of the straight parallel flow field (SPFF), and the power density reaches 0.65 W cm^?2. BAFF improves performance by equalizing the pressure drop across sub-channels, promoting the uniform distribution of reactant, and enhancing transport across the ribs. In addition, through parameter analysis, it is found that BAFF can discharge liquid water in time at the conditions of high humidification, high current density and low temperature, which ensures the output performance of the fuel cell and improves the durability of the fuel cell. This paper provides new ideas for the improvement of PEMFC flow field design, which is beneficial to the development of PEMFC with high current density.     

Pore network modeling of fibrous gas diffusion layers for polymer electrolyte membrane fuel cells

A pore network model of the gas diffusion layer (GDL) in a polymer electrolyte membrane fuel cell is developed and validated. The model idealizes the GDL as a regular cubic network of pore bodies and pore throats following respective size distributions. Geometric parameters of the pore network model are calibrated with respect to porosimetry and gas permeability measurements for two common GDL materials and the model is subsequently used to compute the pore-scale distribution of water and gas under drainage conditions using an invasion percolation algorithm. From this information, the relative permeability of water and gas and the effective gas diffusivity are computed as functions of water saturation using resistor-network theory. Comparison of the model predictions with those obtained from constitutive relationships commonly used in current PEMFC models indicates that the latter may significantly overestimate the gas phase transport properties. Alternative relationships are suggested that better match the pore network model results. The pore network model is also used to calculate the limiting current in a PEMFC under operating conditions for which transport through the GDL dominates mass transfer resistance. The results suggest that a dry GDL does not limit the performance of a PEMFC, but it may become a significant source of concentration polarization as the GDL becomes increasingly saturated with water.     

Study on the effect of humidity and stoichiometry on the water saturation of PEM fuel cells

This paper investigates the effects of relative humidity (RH) and stoichiometry of reactants on the water saturation and local transport process in proton exchange membrane fuel cells. A two‐dimensional model was developed, taking into account the effect of the formation of liquid water on the reactant transport. The results indicate that the reactant RH and stoichiometry significantly affect cell performance. At a constant anode RH = 100%, a lower cathode RH maintains membrane hydration to give better cell performance. At a constant cathode RH = 100%, a lower anode RH not only provides more hydrogen to the catalyst layer to participate in the electrochemical reaction but also increases the difference in the water concentrations between the anode and cathode. This enhances the back‐diffusion of water from the cathode to the anode, reducing possible flooding for better cell performance. Higher anodic stoichiometry results in the reduction of cathodic water saturation by increasing water back‐diffusion, thereby enhancing fuel cell performance. Higher cathodic stoichiometry also reduces water saturation by drying more liquid water to increase cathode local current density. Copyright © 2011 John Wiley & Sons, Ltd.     

Polarization characteristics and property distributions of a proton exchange membrane fuel cell under cathode starvation conditions

Property distribution and polarization characteristics of a proton exchange membrane fuel cell (PEMFC) under cathode starvation conditions were investigated numerically and experimentally for a unit cell. The polarization curves of a lab‐scale PEMFC were measured with increasing current density for different cell temperatures (40°C, 50°C, and 60°C) at a relative humidity of 100%. To investigate the local temperature, water content and current density on the membrane, and gas velocity in the channel of the PEMFC, numerical studies using the es‐pemfc module of the commercial flow solver STAR‐CD, which were matched with experimental data, were conducted. Temperature, current density on the membrane, and water content in the MEA were examined to investigate the effect of cell temperature on performance under the cathode starvation condition. At cathode starvation conditions, the performance of a higher cell temperature condition might drop significantly and the mean temperature on the membrane increase abruptly with increasing cell temperature or current density. Copyright © 2009 John Wiley & Sons, Ltd.     

A novel three-dimensional, two-phase and non-isothermal numerical model for proton exchange membrane fuel cell

A three-dimensional, two-phase and non-isothermal model of a proton exchange membrane fuel cell (PEMFC) based on the previously developed model is established using the two-fluid method. This two-phase model considers the liquid water transport in both cathode and anode sides and accounts for the intrinsic heat transfer between the reactant fluids and the solid matrices. The latent heat of water condensation/evaporation is considered in the present model. The numerical results demonstrate that the lower cathode humidity is beneficial for cell performance. In the anode side, the water vapor can be condensed at high current density because the water vapor transport is less than the hydrogen consumption rate. Near the catalyst layer, the reactant fluid temperature is higher than the solid matrix temperature, and far from the catalyst layer, the temperature difference between the reactant fluid and the solid matrix decreases. Near the channel, the reactant fluid temperature is lower than the solid matrix temperature.     

Review of hydrogen crossover through the polymer electrolyte membrane

Proton exchange membrane fuel cell (PEMFC) is considered to be a promising, clean, and efficient energy conversion device. At present, the main challenges faced by the application of PEMFC in the automotive are cost and durability. Hydrogen from anode to the cathode through polymer electrolyte membrane (i.e. crossover hydrogen) affects the durability of fuel cells. In this paper, the existing literature on hydrogen crossover is reviewed and summarized from consequences, causes, mitigation measures, and detection methods. The influences of hydrogen crossover on the components and performance are discussed. The causes are analyzed from structural permeation and membrane degradation. The methods of alleviating the degradation of the membrane are summarized. The electrochemical and non-electrochemical monitoring methods are described, and the segmented current method is explained separately. The existing problems and research prospects are put forward, which lays a foundation for further research on hydrogen crossover and improvement fuel cell durability.     

Reduction of hydrogen peroxide production at anode of proton exchange membrane fuel cell under open-circuit conditions using ruthenium–carbon catalyst

This study examines the effect of hydrogen peroxide (H₂O₂) on the open-circuit voltage (OCV) of a proton exchange membrane fuel cell (PEMFC) and the reduction of H₂O₂ in the membrane using a ruthenium/carbon catalyst (Ru/C) at the anode. Each cathode and anode potential of the PEMFC in the presence of H₂O₂ is examined by constructing a half-cell using 1.0 M H₂SO₄ solution as an electrolyte and Ag/AgCl as the reference electrode. H₂O₂ is added to the H₂SO₄ solution and the half-cell potential is measured at each H₂O₂ concentration. The cathode potential is affected by the H₂O₂ concentration while the anode potential remains stable. A Ru catalyst is used to reduce the level of H₂O₂ formation through O₂ cross-over at the interface of a membrane and the anode. The Ru catalyst is known to produce less H₂O₂ through oxygen reduction at the anode of PEMFC than a Pt catalyst. A Ru/C layer is placed between the Nafion^® 112 membrane and anode catalyst layer and the cell voltage under open-circuit condition is measured. A single cell is constructed to compare the OCV of the Pt/C only anode with that of the Ru/C-layered anode. The level of hydrogen cross-over and the OCV are determined after operation at a current density of 1 A cm⁻² for 10 h and stabilization at open-circuit for 1 h to obtain an equilibrium state in the cell. Although there is an increase in the OCV of the cell with the Ru/C layer at the anode, excessive addition of Ru/C has an adverse effect on cell performance.     

Numerical investigation on the performance of proton exchange membrane fuel cells with channel position variation

Such factors as mole fractions of species, water generation, and conductivity influence the performance of proton exchange membrane fuel cells (PEMFCs). The geometrical shape of the fuel cells also should be considered a factor in predicting the performance because this affects the species' reaction speed and distribution. Specifically, the position between the channel and rib is an important factor influencing PEMFC performance because the current density distribution is affected by the channel and rib position. Three main variables that decide the current density distribution are selected in the paper: species concentration, overpotentials, and membrane conductivity. These variables should be considered simultaneously in deciding the current density distribution with the given PEMFC cell voltage. In addition, the inlet relative humidity is another factor affecting current density distribution and membrane conductivity. In this paper, two channel‐to‐rib models, namely, channel‐to‐channel and the channel‐to‐rib, are considered for comparing the PEMFC performance. Thorough performance comparisons between these two models are presented to explain which is better under certain parameters. A three‐dimensional numerical PEMFC model is developed for obtaining the current density distribution. Water transfer mechanism because of electro osmotic drag and concentration diffusion also is presented to explain the PEMFC performance comparison between the two models. Copyright © 2012 John Wiley & Sons, Ltd.     

Numerical investigation of liquid water distribution in the cathode side of proton exchange membrane fuel cell and its effects on cell performance

A three-dimensional unsteady two-phase model for the cathode side of proton exchange membrane fuel cell (PEMFC) consisting of gas diffusion layer (GDL) with hybrid structural model is developed to investigate liquid water behaviors under different operating and geometrical conditions and to quantitatively evaluate effects of liquid water distribution on reactant transport and current density distribution. Simulation results reveal that liquid water transport processes and distributions are significantly affected by inlet air velocity, wall wettability and water inlet position, which in turn play a prominent role on local reactant transport and cause considerable disturbances of the current density. Liquid water film spreading on the gas channel (GC) top wall is identified as the most desirable flow pattern in the GC based on overall evaluations of current density magnitude, uniformity of current density distribution and pressure drop in the GC. Modification to GDL structure is proposed to promote the formation of the desirable flow pattern.     

The impact of channel path length on PEMFC flow-field design

Distributions in reactant species concentration in a PEMFC due to local consumption of fuel and local transport of water through the membrane cause distributions in current density, temperature, and water concentration in three dimensions in a PEMFC. These distributions can lead to flooding or drying of the membrane that may shorten the life of an MEA. Changing the cell's flow-field pattern to distribute the gas more evenly is one method of minimizing these stresses. This paper investigates how 200 cm² serpentine flow-fields with different number of gas paths, and thus different gas path lengths, affect performance and species distribution. The results show how the local temperature, water content, and current density distributions become more uniform for serpentine flow-field designs with shorter path lengths or larger number of channels. These results may be used to develop universal heuristics and dimensionless number correlations in the design of flow-fields and stacks.     

Numerical simulation of exchange membrane fuel cells in different operating conditions

A two-dimensional, steady state model for proton exchange membrane fuel cell (PEMFC) is presented. The model is used to describe the effect operation conditions (current density, pressure and water content) on the water transport, ohmic resistance and water distribution in the membrane and performance of PEMFC. This model considers the transport of species and water along the porous media: gas diffusion layers (GDL) anode and cathode, and the membrane of PEMFC fuel cell.     

Dynamic characteristics of local current densities and temperatures in proton exchange membrane fuel cells during reactant starvations

Reactant starvation during proton exchange membrane fuel cell (PEMFC) operation can cause serious irreversible damages. In order to study the detailed local characteristics of starvations, simultaneous measurements of the dynamic variation of local current densities and temperatures in an experimental PEMFC with single serpentine flow field have been performed during both air and hydrogen starvations. These studies have been performed under both current controlled and cell voltage controlled operations. It is found that under current controlled operations cell voltage can decrease very quickly during reactant starvation. Besides, even though the average current is kept constant, local current densities as well as local temperatures can change dramatically. Furthermore, the variation characteristics of local current density and temperature strongly depend on the locations along the flow channel. Local current densities and temperatures near the channel inlet can become very high, especially during hydrogen starvation, posing serious threats for the membrane and catalyst layers near the inlet. When operating in a constant voltage mode, no obvious damaging phenomena were observed except very low and unstable current densities and unstable temperatures near the channel outlet during hydrogen starvation. It is demonstrated that measuring local temperatures can be effective in exploring local dynamic performance of PEMFC and the thermal failure mechanism of MEA during reactants starvations.