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.     

Three‐dimensional optimisation of a fuel gas channel of a proton exchange membrane fuel cell for maximum current density

Proton exchange membrane (PEM) fuel cells operated with hydrogen and air offer promising alternative to conventional fossil fuel sources for transport and stationary applications because of its high efficiency, low‐temperature operation, high power density, fast start‐up and potable power for mobile application. Power levels derivable from this class of fuel cell depend on the operating parameters. In this study, a three‐dimensional numerical optimisation of the effect of operating and design parameters of PEM fuel cell performance was developed. The model computational domain includes an anode flow channel, membrane electrode assembly and a cathode flow channel. The continuity, momentum, energy and species conservation equations describing the flow and species transport of the gas mixture in the coupled gas channels and the electrodes were numerically solved using a computational fluid dynamics code. The effects of several key parameters, including channel geometries (width and depth), flow orientation and gas diffusion layer (GDL) porosity on performance and species distribution in a typical fuel cell system have been studied. Numerical results of the effect of flow rate and GDL porosity on the flow channel optimal configurations for PEM fuel cell are reported. Simulations were carried out ranging from 0.6 to 1.6 mm for channel width, 0.5 to 3.0 mm for channel depth and 0.1 to 0.7 for the GDL porosity. Results were evaluated at 0.3 V operating cell voltage of the PEM fuel cell. The optimisation results show that the optimum dimension values for channel depth and channel width are 2.0 and 1.2 mm, respectively. In addition, the results indicate that effective design of fuel gas channel in combination with the reactant species flow rate and GDL porosity enhances the performance of the fuel cell. The numerical results computed agree well with experimental data in the literature. Consequently, the results obtained provide useful information for improving the design of fuel cells. Copyright © 2011 John Wiley & Sons, Ltd.     

On the relative influence of convection in serpentine flow fields of PEM fuel cells

In polymer electrolyte membrane fuel cells, power losses associated with slow reaction kinetics and mass-transport limits can be strongly influenced by convective flow characteristics. Specifically, convection in the form of channel bypass may be utilized to simultaneously increase reactant concentration and reduce product concentration in the catalyst layer, thus reducing the activation and mass-transport overpotentials. An analytical model is developed here to predict the flow pattern and pressure field in general single-serpentine flow field geometries. The model predicts that a significant portion of the total flow through the fuel cell can occur as in-plane convective flow through the gas diffusion layer under realistic operating conditions. Further, by comparing the in-plane rates of diffusive and convective transport it is found that the dominant mechanism depends on the geometric and material parameters of the flow field. In particular, it is found that the relative influence of convection depends highly on in-plane permeability of the gas diffusion layer and channel length, and is relatively independent of gas diffusion layer thickness. By designing fuel cells to utilize enhanced in-plane convection, it is suggested that losses associated with low oxygen content as well as liquid water buildup in the catalyst layer can be reduced.     

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.     

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.     

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.     

Experimental investigation of liquid water formation and transport in a transparent single-serpentine PEM fuel cell

Liquid water formation and transport were investigated by direct experimental visualization in an operational transparent single-serpentine PEM fuel cell. We examined the effectiveness of various gas diffusion layer (GDL) materials in removing water away from the cathode and through the flow field over a range of operating conditions. Complete polarization curves as well as time evolution studies after step changes in current draw were obtained with simultaneous liquid water visualization within the transparent cell. The level of cathode flow field flooding, under the same operating conditions and cell current, was recognized as a criterion for the water removal capacity of the GDL materials. When compared at the same current density (i.e. water production rate), higher amount of liquid water in the cathode channel indicated that water had been efficiently removed from the catalyst layer.

Visualization of the anode channel was used to investigate the influence of the microporous layer (MPL) on water transport. No liquid water was observed in the anode flow field unless cathode GDLs had an MPL. MPL on the cathode side creates a pressure barrier for water produced at the catalyst layer. Water is pushed across the membrane to the anode side, resulting in anode flow field flooding close to the H₂ exit.     

Effects of electrode wettabilities on liquid water behaviours in PEM fuel cell cathode

Liquid water transport is one of the key challenges for water management in a proton exchange membrane (PEM) fuel cell. Investigation of the air–water flow patterns inside fuel cell gas flow channels with gas diffusion layer (GDL) would provide valuable information that could be used in fuel cell design and optimization. This paper presents numerical investigations of air–water flow across an innovative GDL with catalyst layer and serpentine channel on PEM fuel cell cathode by use of a commercial Computational Fluid Dynamics (CFD) software package FLUENT. Different static contact angles (hydrophilic or hydrophobic) were applied to the electrode (GDL and catalyst layer). The results showed that different wettabilities of cathode electrode could affect liquid water flow patterns significantly, thus influencing on the performance of PEM fuel cells. The detailed flow patterns of liquid water were shown, several gas flow problems were observed, and some useful suggestions were given through investigating the flow patterns.     

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.     

Liquid water transport between graphite paper and a solid surface

We studied the interaction of a water droplet with a solid wall on a hydrophobic gas diffusion layer (GDL). Of particular interest is the stability of the droplet as a function of plate wetting properties and the potential for liquid entrapment in the GDL/land contact area. Such transport is of relevance to breakthrough dynamics and convective liquid droplet transport in polymer electrolyte membrane (PEM) fuel cell cathode gas channels. While a variety of complex coupled transport phenomena are present in the PEM fuel cell gas channel, we utilize a very simplified experimental model of the system where a droplet originally placed on a hydrophobic GDL is translated quasistatically across the GDL surface by a solid surface. Transport and entrapment are imaged using fluorescence microscopy. This work provides new insights into droplet behaviour at the GDL/land interface in a PEM fuel cell and suggests that hydrophobic land areas are preferable for mitigating the accumulation of liquid water under the land area of the gas flow channels.     

Numerical investigation of multi-layered porosity in the gas diffusion layer on the performance of a PEM fuel cell

A mathematical model is developed to investigate the influence of porosity configurations in the gas diffusion layer (GDL) of the cathode on the electrochemical performance characteristics of a 3-D high-temperature proton exchange membrane (PEM) fuel cell. Four different non-uniform porosity configurations are defined through step functions and analyzed with uniform porosity case. The results are presented in terms of the cell performance characteristics viz. Current density, power density, vorticity magnitude, oxygen molar concentration, overpotential, and total power dissipation density. Our study reveals that oxygen molar concentration, current density, power density are found to be maximum when the stepwise porosity in GDL decreases in the streamwise direction. However, these parameters observed to be the least when the stepwise porosity in GDL increases along the streamwise direction. Additionally, the highest total power dissipation density is observed when the porosity in GDL varies across cross-stream wise direction among other configurations considered. However, it is found to be the least when porosity varies in a streamwise direction. The overpotential becomes the least when stepwise porosity decreases in the streamwise direction although the same is found to be maximum when the porosity in GDL increases along the streamwise direction. The performance is found to be optimal when porosity is maximum at cathode gas channel inlet and GDL-cathode gas channel interface.     

An investigation of channel blockage effects on hydrogen mass transfer in a proton exchange membrane fuel cell with various geometries and optimization by response surface methodology

A 2D mathematical modeling was developed to analyze the mass transport in a proton exchange membrane fuel cell. The pin fins were inserted in the flow channel to improve reactant gas distribution in the gas diffusion layer (GDL). The effect of rectangular and triangular shape of fins and different title angles of 4, 6 and 8° on the reactant gas transport were examined. The results showed that performance of rectangular fins are better than triangular fins due to increasing reactant spread over the GDL. The effect of three independent factors including length and width of blocks and hydrogen gas velocity on the response (hydrogen gas diffusion to GDL and pressure drop in anode channel) was investigated using analysis of variance (ANOVA). The results showed that block height and hydrogen gas velocity are the most important factors affecting the responses. Also, response surface methodology (RSM) method was used to predict the optimal conditions to achieve the minimum the pressure drop and maximum the total flux magnetic H₂ to GDL in anode channel. The result of the optimization process shows that a gas velocity of 4.22 m/s and the block with height and width of 3 mm are the optimal conditions.     

Performance evaluation of passive direct methanol fuel cell with methanol vapour supplied through a flow channel

This work examines the effect of fuel delivery configuration on the performance of a passive air-breathing direct methanol fuel cell (DMFC). The performance of a single cell is evaluated while the methanol vapour is supplied through a flow channel from a methanol reservoir connected to the anode. The oxygen is supplied from the ambient air to the cathode via natural convection. The fuel cell employs parallel channel configurations or open chamber configurations for methanol vapour feeding. The opening ratio of the flow channel and the flow channel configuration is changed. The opening ratio is defined as that between the area of the inlet port and the area of the outlet port. The chamber configuration is preferred for optimum fuel feeding. The best performance of the fuel cell is obtained when the opening ratio is 0.8 in the chamber configuration. Under these conditions, the peak power is 10.2 mW cm⁻² at room temperature and ambient pressure. Consequently, passive DMFCs using methanol vapour require sufficient methanol vapour feeding through the flow channel at the anode for best performance. The mediocre performance of a passive DMFC with a channel configuration is attributed to the low differential pressure and insufficient supply of methanol vapour.     

Two-phase flow and maldistribution in gas channels of a polymer electrolyte fuel cell

Liquid water transport in a polymer electrolyte fuel cell (PEFC) is a major issue for automotive applications. Mist flow with tiny droplets suspended in gas has been commonly assumed for channel flow while two-phase flow has been modeled in other cell components. However, experimental studies have found that two-phase flow in the channels has a profound effect on PEFC performance, stability and durability. Therefore, a complete two-phase flow model is developed in this work for PEFC including two-phase flow in both anode and cathode channels. The model is validated against experimental data of the wetted area ratio and pressure drop in the cathode side. Due to the intrusion of soft gas diffusion layer (GDL) material in the channels, flow resistance is higher in some channels than in others. The resulting flow maldistribution among PEFC channels is of great concern because non-uniform distributions of fuel and oxidizer result in non-uniform reaction rates and thus adversely affect PEFC performance and durability. The two-phase flow maldistribution among the parallel channels in an operating PEFC is explored in detail.     

Cathode flooding behaviour in alkaline direct ethanol fuel cells

In an alkaline fuel cell, such as a direct ethanol fuel cell (DEFC), owing to the fact that water is consumed as a reactant at the cathode and the electro-osmotic drag (EOD) moves water from the cathode to the anode, a conventional conception is that the cathode flooding is unlikely. In this work, however, it is shown experimentally that cathode flooding also occurs in an alkaline DEFC, primarily because of the fact that the diffusion flux from the anode to the cathode outweighs the total water flux due to both the oxygen reduction reaction and EOD. More interestingly, rather than in acid electrolyte based fuel cells where the cathode flooding occurs at a high (limiting) current, in an alkaline DEFC the cathode flooding occurs at an intermediate current.     

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.     

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.     

In-situ measurements of GDL effective permeability and under-land cross-flow in a PEM fuel cell

When reactant gases flow along a channel in serpentine flow field of a proton exchange membrane (PEM) fuel cell, there is a pressure difference between the adjacent channels and it produces an under-land cross-flow (or under-rib convection) from the higher pressure side to the lower pressure side through the gas diffusion layer (GDL). A unique experimental setup is developed for in-situ measurement of this cross-flow and the GDL effective permeability at the cathode side of a PEM fuel cell under dry and realistic humidified gas conditions. The non-Darcy effect, defined as a function of the Forchheimer number is studied and compared for both 1 mm and 2 mm land widths and both dry and humidified air conditions. Finally, a dimensional analysis is performed and the non-dimensional cross-flowrate is shown to increases linearly with the increase of the non-dimensional pressure difference.     

Review on water management methods for proton exchange membrane fuel cells

Control of water content of proton exchange membrane fuel cells (PEMFCs) within a reasonable rangeis a question worthy of study. This paper addresses questions of water transport, water fault, and water management methods in a PEMFC. Both an excess (overflow) or lack (dehydration) of water in a fuel cell may affect the performance and the service life. Herein, we describe in detail the effects of water content on the cathode, anode, gas diffusion layer (GDL), catalyst layer (CL) and flow channel. Monitoring the flow and accumulation of water directly in the PEMFC is the most effective approach to determine which of the two scenarios, overflow or dehydration, occurs. The water transport can be effectively investigated in a transparent fuel cell, using neutron scanning, nuclear magnetic resonance, and X-ray irradiation. Regarding the PEMFC water management, this paper reviews some current methods, such as improvement of the flow field structure, changing hydrophilic materials, and optimizing control systems.     

Simultaneous measurement of current and temperature distributions in a proton exchange membrane fuel cell

Using a specially designed current distribution measurement gasket in anode and thin thermocouples between the catalyst layer and gas diffusion layer (GDL) in cathode, in-plane current and temperature distributions in a proton exchange membrane fuel cell (PEMFC) have been simultaneously measured. Such simultaneous measurements are realized in a commercially available experimental PEMFC. Experiments have been conducted under different air flow rates, different hydrogen flow rates and different operating voltages, and measurement results show that there is a very good correlation between local temperature rise and local current density. Such correlations can be explained and agree well with basic thermodynamic analysis. Measurement results also show that significant difference exists between the temperatures at cathode catalyst layer/GDL interface and that in the center of cathode endplate, which is often taken as the cell operating temperature. Compared with separate measurement of local current density or temperature, simultaneous measurements of both can reveal additional information on reaction irreversibility and various transport phenomena in fuel cells.