Numerical investigations of effect of membrane electrode assembly structure on water crossover in a liquid-feed direct methanol fuel cell

A two-phase mass-transport model is employed to investigate the water transport behaviour through the membrane electrode assembly (MEA) of a liquid-feed direct methanol fuel cell (DMFC). Emphasis is placed on examining the effects of each constituent component design of the MEA, including catalyst layers, microporous layers and membranes, on each of the three water crossover mechanisms: electro-osmotic drag, diffusion, and convection. The results show that lowering the diffusion flux of water or enhancing the convection flux of water (termed as the back-flow flux) through the membrane are both feasible to suppress water crossover in DMFCs. It is found that the reduction in the diffusion flux of water can be mainly achieved through optimum design of the anode porous layers, as the effect of the cathode porous region on water crossover by diffusion is relatively smaller. On the other hand, the design of the cathode porous layers plays a more important role in increasing the back-flow flux of water from the cathode to anode.     

Small direct methanol fuel cells with passive supply of reactants

Small, stand-alone, direct methanol fuel cells (DMFCs) that have no auxiliary liquid pumps and gas blowers/compressors are known as passive DMFCs. The devices are ideal for powering portable electronic devices, as this type of fuel cell uniquely has a simple and compact system and no parasitic power losses. This article provides a comprehensive review of experimental and numerical studies of heat and mass transport in passive DMFCs. Emphasis is placed on the mechanisms and key issues of the mass transport of each species through the fuel cell structure under the influence of passive forces. It is shown that the key issue regarding the methanol supply is how to feed high-concentration methanol solution but with minimum methanol crossover through the membrane so that both the system specific energy and cell performance can be maximized. The key issue regarding the oxygen supply is how to enhance the removal of liquid water from the cathode under the air-breathing condition. For water transport, the aim is to transport the water produced on the cathode through the membrane to the anode by optimizing the design of the membrane electrode assembly so that the fuel cell can be operated with pure methanol and with minimum flooding at the cathode. The heat loss from a passive DMFC is usually large and it is therefore critically important to reduce this feature so that the fuel cell can be operated at a sufficiently high temperature, which critically affects the cell performance.     

Analysis of an active tubular liquid-feed direct methanol fuel cell

A two-dimensional, two-phase, non-isothermal model was developed for an active, tubular, liquid-feed direct methanol fuel cell (DMFC). The liquid-gas, two-phase mass transport in the porous anode and cathode was formulated based on the multi-fluid approach in the porous media. The two-phase mass transport in the anode and cathode channels was modeled using the drift-flux and the homogeneous mist-flow models, respectively. Water and methanol crossovers through the membrane were considered due to the effects of diffusion, electro-osmotic drag, and convection. The model enabled a numerical investigation of the effects of various operating parameters, such as current density, methanol flow rate, and oxygen flow rate, on the mass and heat transport characteristics in the tubular DMFC. It was shown that by choosing a proper tube radius and distance between the adjacent cells, a tubular DMFC stack can achieve a much higher energy density compared to its planar counterpart. The results also showed that a large anode flow rate is needed in order to avoid severe blockage of liquid methanol to the anode electrode due to the gas accumulation in the channel. Besides, lowering the flow rate of either the methanol solution or air can lead to a temperature increase along the flow channel. The methanol and water crossovers are nearly independent of the methanol flow rate and the air flow rate.     

Water management in direct methanol fuel cells

Water management is an important challenge in portable direct methanol fuel cells. Reducing the water and methanol loss from the anode to the cathode enables the use of highly concentrated methanol solutions to achieve enhanced performances. In this work, the results of a simulation study using a previous developed model for DMFCs are presented. Particular attention is devoted to the water distribution across the cell. The influence of different parameters (such as the cathode relative humidity (RH), the methanol concentration and the membrane, catalyst layer and diffusion media thicknesses) over the water transport and on the cell performance is studied. The analytical solutions of the net water transport coefficient, for different values of the cathode relative humidity are successfully compared with recent published experimental data putting in evidence that humidified cathodes contribute to a decrease on the water crossover. As a result of the modelling results, a tailored MEA build-up with the common available commercial materials is proposed to achieve low methanol and water crossover and high power density, operating at relatively high methanol concentrations. A thick anode catalyst layer to promote methanol oxidation, a thin anode gas diffusion layer as methanol carrier to the catalyst layer and a thin polymer membrane to lower the water crossover coefficient between the anode and cathode are suggested.     

Water transport characteristics in a passive liquid-feed DMFC

A two-dimensional, two-phase, non-isothermal model was developed to investigate the water transport characteristics in a passive liquid-feed direct methanol fuel cell (DMFC). The liquid–gas two-phase mass transport in the porous anode and cathode was formulated based on multi-fluid model in porous media, and water and methanol crossover through the membrane were considered with the effect of diffusion, electro-osmotic drag, and convection. The model enabled numerical investigation of the effects of various operating parameters, such as current density, methanol concentration, and air humidity, as well as the effect of the cathode hydrophobic air filter layer, on the water transport and cell performance. The results showed that for the free-breathing cathode, gas species concentration and temperature showed evident differences between the cell and the ambient air. The use of a hydrophobic air filter layer at the cathode helped to achieve water recovery from the cathode to the anode, although the oxygen transport resistance was increased to some extent. It was further revealed that the water transport can be influenced by the ambient relative humidity.     

Characteristics of water transport through the membrane in direct methanol fuel cells operating with neat methanol

The water required for the methanol oxidation reaction in a direct methanol fuel cell (DMFC) operating with neat methanol can be supplied by diffusion from the cathode to the anode through the membrane. In this work, we present a method that allows the water transport rate through the membrane to be in-situ determined. With this method, the effects of the design parameters of the membrane electrode assembly (MEA) and operating conditions on the water transport through the membrane are investigated. The experimental data show that the water flux by diffusion from the cathode to the anode is higher than the opposite flow flux of water due to electro-osmotic drag (EOD) at a given current density, resulting in a net water transport from the cathode to the anode. The results also show that thinning the anode gas diffusion layer (GDL) and the membrane as well as thickening the cathode GDL can enhance the water transport flux from the cathode to the anode. However, a too thin anode GDL or a too thick cathode GDL will lower the cell performance due to the increases in the water concentration loss at the anode catalyst layer (CL) and the oxygen concentration loss at the cathode CL, respectively.     

An approach for determining the liquid water distribution in a liquid-feed direct methanol fuel cell

In determining the liquid water distribution in the anode (or the cathode) diffusion medium of a liquid-feed direct methanol fuel cell (DMFC) with a conventional two-phase mass transport model, a current-independent liquid saturation boundary condition at the interface between the anode flow channel and diffusion layer (DL) (or at the interface between the cathode flow channel and cathode DL) needs to be assumed. The numerical results resulting from such a boundary condition cannot realistically reveal the liquid distribution in the porous region, as the liquid saturation at the interface between the flow channel and DL varies with current density. In this work, we propose a simple theoretical approach that is combined with the in situ measured water-crossover flux in the DMFC to determine the liquid saturation in the anode catalyst layer (CL) and in the cathode CL. The determined liquid saturation in the anode CL (or in the cathode CL) can then be used as a known boundary condition to determine the water distribution in the anode DL (or in the cathode DL) with a two-phase mass transport model. The numerical results show that the water distribution becomes much more realistic than those predicted with the assumed boundary condition at the interface between the flow channel and DL.     

High concentration methanol fuel cells: Design and theory

Use of highly concentrated methanol fuel is required for direct methanol fuel cells (DMFCs) to compete with the energy density of Li-ion batteries. Because one mole of H₂O is needed to oxidize one mole of methanol (CH₃OH) in the anode, low water crossover to the cathode or even water back flow from the cathode into the anode is a prerequisite for using highly concentrated methanol. It has previously been demonstrated that low or negative water crossover can be realized by the incorporation of a low-α membrane electrode assembly (MEA), which is essentially an MEA designed for optimal water management, using, e.g. hydrophobic anode and cathode microporous layers (aMPL and cMPL). In this paper we extend the low-α MEA concept to include an anode transport barrier (aTB) between the backing layer and hydrophobic aMPL. The main role of the aTB is to act as a barrier to CH₃OH and H₂O diffusion between a water-rich anode catalyst layer (aCL) and a methanol-rich fuel feed. The primary role of the hydrophobic aMPL in this MEA is to facilitate a low (or negative) water crossover to the cathode. Using a previously developed 1D, two-phase DMFC model, we show that this novel design yields a cell with low methanol crossover (i.e. high fuel efficiency, ∼80%, at a typical operating current density of ∼80-90% of the cell limiting current density), while directly feeding high concentration methanol fuel into the anode. The physics of how the aTB and aMPL work together to accomplish this is fully elucidated. We further show that a thicker, more hydrophilic, more permeable aTB, and thicker, more hydrophobic, and less permeable aMPL are most effective in accomplishing low CH₃OH and H₂O crossover.     

Effect of design of multilayer electrodes in direct methanol fuel cells (DMFCs)

In a direct methanol fuel cell (DMFC), optimized multilayer electrode design is critical to mitigate methanol crossover and improve cell performance. In this paper, we present a one-dimensional (1-D) two-phase model based on the saturation jump theory in order to explore the methanol and water transport characteristics using various multilayer electrode configurations. To experimentally validate the 1-D model, two different membrane electrode assemblies (MEAs) with and without an anode microporous layer (MPL) are fabricated and tested under various cell current density and methanol feed concentration conditions. Then, 1-D DMFC simulations are performed and the results compared to the experimental data. In general, the numerical predictions are in good agreement with the experimental data; thus, the 1-D DMFC simulations successfully model the effects of the anode MPL that were observed experimentally. In addition to the comparison study, additional numerical simulations are carried out to precisely examine the role of the anode and cathode MPLs and the effect of the hydrophobicity of the anode catalyst layer on the water and liquid saturation distributions inside the DMFCs. This paper demonstrates the quantitative accuracy of the saturation jump model for simulating multilayer DMFC MEAs and also provides greater insight into the operational characteristics of DMFCs incorporating multilayer electrodes.     

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.     

Numerical study of the effect of the GDL structure on water crossover in a direct methanol fuel cell

A two-dimensional two-phase non-isothermal mass transport model is developed to numerically investigate the behavior of water transport through the membrane electrode assembly (MEA) of a direct methanol fuel cell. The model enables the visualization of the distribution of the liquid saturation through the MEA and the analysis of the distinct effects of the three water transport mechanisms: diffusion, convection and electro-osmotic drag, on the water-crossover flux through the membrane. A parametric study is then performed to examine the effects of the structure design of the gas diffusion layer (GDL) on water crossover. The results indicate that the flow-channel rib coverage on the GDL surface and the deformation of the GDL can cause an uneven distribution of the water-crossover flux along the in-plane direction, especially at higher current densities. It is also found that both the contact angle and the permeability of the cathode GDL can significantly influence the water-crossover flux. The water-crossover flux can be reduced by improving the hydrophobicity of the cathode GDL.     

A one-dimensional,two-phase model for direct methanol fuel cells – Part I: Model development and parametric study

A one-dimensional, steady-state, two-phase direct methanol fuel cell (DMFC) model is developed to precisely investigate complex physiochemical phenomena inside DMFCs. In this model, two-phase species transport through the porous components of a DMFC is formulated based on Maxwell–Stefan multi-component diffusion equations, while capillary-induced liquid flow in the porous media is described by Darcy's equation. In addition, the model fully accounts for water and methanol crossover through the membrane, which is driven by the effects of electro-osmotic drag, diffusion, and the hydraulic pressure gradient. The developed model is validated against readily available experimental data in the literature. Then, a parametric study is carried out to investigate the effects of the operating temperature, methanol feed concentration, and properties of the backing layer. The results of the numerical simulation clarify the detailed influence of these key designs and operating parameters on the methanol crossover rate as well as cell performance and efficiency. The results emphasize that the material properties and design of the anode backing layer play a critical role in the use of highly concentrated methanol fuel in DMFCs. The present study forms a theoretical background for optimizing the DMFC's components and operating conditions.     

Stable operation of air-blowing direct methanol fuel cells with high performance

A membrane electrode assembly (MEA) that is a combination of a catalyst-coated membrane (CCM) for the anode and a catalyst-coated substrate (CCS) for the cathode is studied under air-blower conditions for direct methanol fuel cells (DMFCs). Compared with MEAs prepared by only the CCS method, the performance of DMFC MEAs employing the combination method is significantly improved by 30% with less methanol crossover. This feature can be attributed to an enhanced electrode|membrane interface in the anode side and significantly higher catalyst efficiency. Furthermore, DMFC MEAs designed by the combination method retain high power density without any degradation, while the CCM-type cell shows a downward tendency in electrochemical performance under air-blower conditions. This may be due to MEAs with CCM have a much more difficult structure of catalytic active sites in the cathode to eliminate the water produced by electrochemical reaction. In addition, DMFCs produced via combination methods exhibit a lower water crossover flux than CCS alternatives, due to the comparatively dense structure of the CCM anode. Hence, DMFCs with a combination MEA structure demonstrate the feasibility of a small fuel cell system employing the low noise of a fan, instead of a noisy and large capacity air pump, for portable electronic devices.     

Mass balance research for high electrochemical performance direct methanol fuel cells with reduced methanol crossover at various operating conditions

Mass balance research in direct methanol fuel cells (DMFCs) provides a more practical method in characterizing the mass transport phenomena in a membrane electrode assembly (MEA). This method can be used to measure methanol utilization efficiency, water transport coefficient (WTC), and methanol to electricity conversion rate of a MEA in DMFCs. First, the vital design parameters of a MEA are recognized for achieving high methanol utilization efficiency with increased power density. In particular, the structural adjustment of anode diffusion layer by adding microporous layer (MPL) is a very effective way to decrease WTC with reduced methanol crossover due to the mass transfer limitation in the anode. On the other hand, the cathode MPL in the MEA design can contribute in decreasing methanol crossover. The change of structure of cathode diffusion layer is also found to be a very effective way in improving power density. In contrast, the WTC of DMFC MEAs remains virtually constant in the range of 3.4 and 3.6 irrespective of the change of the cathode GDL. The influence of operating condition on the methanol utilization efficiency, WTC, and methanol to electricity conversion rate is also presented and it is found that these mass balance properties are strongly affected by temperature, current density, methanol concentration, and the stoichiometry of fuel and air.     

Quantifying water transport in anion exchange membrane fuel cells

Sufficient water transport through the membrane is necessary for a well-performing anion exchange membrane fuel cell (AEMFC). In this study, the water flux through a membrane electrode assembly (MEA), using a Tokuyama A201 membrane, is quantified using humidity sensors at the in- and outlet on both sides of the MEA. Experiments performed in humidified inert gas at both sides of the MEA or with liquid water at one side shows that the aggregation state of water has a large impact on the transport properties. The water fluxes are shown to be approximately three times larger for a membrane in contact with liquid water compared to vaporous. Further, the flux during fuel cell operation is investigated and shows that the transport rate of water in the membrane is affected by an applied current. The water vapor content increases on both the anode and cathode side of the AEMFC for all investigated current densities. Through modeling, an apparent water drag coefficient is determined to −0.64, indicating that the current-induced transport of water occurs in the opposite direction to the transport of hydroxide ions. These results implicate that flooding, on one or both electrodes, is a larger concern than dry-out in an AEMFC.     

Passive direct methanol fuel cells fed with methanol vapor

A vapor fed passive direct methanol fuel cell (DMFC) is proposed to achieve a high energy density by using pure methanol for mobile applications. Vapor is provided from a methanol reservoir to the membrane electrode assembly (MEA) through a vaporizer, barrier and buffer layer. With a composite membrane of lower methanol cross-over and diffusion layers of hydrophilic nanomaterials, the humidity of the MEA was enhanced by water back diffusion from the cathode to the anode through the membrane in these passive DMFCs. The humidity in the MEA due to water back diffusion results in the supply of water for an anodic electrochemical reaction with a low membrane resistance. The vapor fed passive DMFC with humidified MEA maintained 20–25 mW cm⁻² power density for 360 h and performed with a 70% higher fuel efficiency and 1.5 times higher energy density when compared with a liquid fed passive DMFC.     

A two-dimensional two-phase mass transport model for direct methanol fuel cells adopting a modified agglomerate approach

A two-dimensional two-phase mass transport model for liquid-feed direct methanol fuel cells (DMFCs) is presented in this paper. The fluid flow and mass transport across the membrane electrode assembly (MEA) is formulated based on the classical multiphase flow theory in the porous media. The modeling of mass transport in the catalyst layers (CLs) and membrane is given more attentions. The effect of the two-dimensional migration of protons in the electrolyte phase on the liquid flow behavior is considered. Water and methanol crossovers through the membrane are implicitly calculated in the governing equations of momentum and methanol concentration. A modified agglomerate model is developed to characterize the microstructure of the CLs. A self-written computer code is used to solve the inherently coupled differential governing equations. Then this model is applied to investigate the mechanisms of species transport and the distributions of the species concentrations, overpotential and the electrochemical reaction rates in CLs. The effects of radius and overlapping angle of agglomerates on cell performance are also explored in this work.     

A transient two-phase mass transport model for liquid feed direct methanol fuel cells

A transient two-phase mass transport model for liquid feed direct methanol fuel cells (DMFCs) is developed. With this model, various processes that affect the DMFC transient behaviors are numerically studied. The results show that the cell voltage exhibits an overshoot behavior in response to a sudden change in the current density. The magnitude of the overshoot depends on the magnitudes of the change in the cell current density and the initial current density. It is found that the dynamic change in the methanol permeation through the membrane to the cathode results in a strong cathode overpotential overshoot, which is believed to be the predominant factor that leads to the cell voltage overshoot. In contrast, the anode overpotential is relatively insensitive to the changes in the methanol concentration as well as CO surface coverage in the anode catalyst layer. Moreover, the effect of the double layer capacitance (DLC) on the cell dynamic behavior is studied and the results show that the DLC can smoothen the change in the cell voltage in response to a change in the cell current density. Furthermore, the dynamic response of mass transport to a change in the cell current density is found to be rather slow. In particular, it is shown that the slow response in the mass transport of methanol is one of the key factors that influence the cell dynamic operation.     

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.     

Enhancement of water retention in the membrane electrode assembly for direct methanol fuel cells operating with neat methanol

It is desirable to operate a direct methanol fuel cell (DMFC) with neat methanol to maximize the specific energy of the DMFC system, and hence increasing its runtime. A way to achieve the neat-methanol operation is to passively transport the water produced at the cathode through the membrane to the anode to facilitate the methanol oxidation reaction (MOR). To achieve a performance of the MOR similar to that under the conventional diluted methanol operation, both the water transport rate and the local water concentration in the anode catalyst layer (CL) are required to be sufficiently high. In this work, a thin layer consisting of nanosized SiO₂ particles and Nafion ionomer (referred to as a water retention layer hereafter) is coated onto each side of the membrane. Taking advantage of the hygroscopic nature of SiO₂, the cathode water retention layer can help maintain the water produced from the cathode at a higher concentration level to enhance the water transport to the anode, while the anode retention layer can retain the water that is transported from the cathode. As a result, a higher water transport rate and a higher water concentration at the anode CL can be achieved. The formed membrane electrode assembly (MEA) with the added water retention layers is tested in a passive DMFC and the results show that this MEA design yields a much higher power density than the MEA without water retention layers does.