A single-phase model for liquid-feed DMFCs with non-Tafel kinetics

An isothermal single-phase 3D/1D model for liquid-feed direct methanol fuel cells (DMFC) is presented. Three-dimensional (3D) mass, momentum and species transport in the anode channels and gas diffusion layer is modeled using a commercial, finite-volume based, computational fluid dynamics (CFD) software complemented with user supplied subroutines. The 3D model is locally coupled to a one-dimensional (1D) model accounting for the electrochemical reactions in both the anode and the cathode, which provides a physically sound boundary condition for the velocity and methanol concentration fields at the anode gas diffusion layer/catalyst interface. The 1D model – comprising the membrane–electrode assembly, cathode gas diffusion layer, and cathode channel – assumes non-Tafel kinetics to describe the complex kinetics of the multi-step methanol oxidation reaction at the anode, and accounts for the mixed potential associated with methanol crossover, induced both by diffusion and electro-osmotic drag. Polarization curves computed for various methanol feed concentrations, temperatures, and methanol feed velocities show good agreement with recent experimental results. The spatial distribution of methanol in the anode channels, together with the distributions of current density, methanol crossover and fuel utilization at the anode catalyst layer, are also presented for different opperating conditions.     

A three-dimensional mathematical model for liquid-fed direct methanol fuel cells

A three-dimensional, single-phase, multi-component mathematical model has been developed for a liquid-fed direct methanol fuel cell (DMFC). The traditional continuity, momentum, and species conservation equations are coupled with electrochemical kinetics in both the anode and cathode catalyst layer. At the anode side, the liquid phase is considered, and at the cathode side only the gas phase is considered. Methanol crossover due to both diffusion and electro-osmotic drag from the anode to the cathode is taken into consideration and the effect is incorporated into the model using a mixed-potential at the cathode. A finite-volume-based CFD technique is used to develop the in-house numerical code and the code is successfully used to simulate the fuel cell performance as well as the multi-component behavior in a DMFC. The modeling results of polarization curves compare well with our experimental data. Subsequently, the model is used to study the effects of methanol crossover, the effects of porosities of the diffusion layer and the catalyst layer, the effects of methanol flow rates, and the effects of the channel shoulder widths.     

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.     

Transient and steady-state analysis of catalyst poisoning and mixed potential formation in direct methanol fuel cells

The present dynamic model is developed to investigate the coupled reaction mechanisms in a DMFC and therein associated voltage losses in the catalyst layers. The model describes a complete five-layer membrane electrode assembly (MEA), with gas diffusion layers, catalyst layers and membrane. The analysis of the performance losses are mainly focused on the electrochemical processes. The model accounts for the crossover of both, methanol from anode to cathode and oxygen from cathode to anode. The reactant crossover results in parasitic internal currents that are finally responsible for high overpotentials in both electrodes, so-called mixed potentials. A simplified and general reaction mechanism for the methanol oxidation reaction (MOR) was selected, that accounts for the coverage of active sites by intermediate species occurring during the MOR. The simulation of the anode potential relaxation after current interruption shows an undershoot behavior like it was measured in the experiment [1]. The model gives an explanation of this phenomenon by the transients of reactant crossover in combination with the change of CO and OH coverages on Pt and Ru, respectively.     

Experimental validation of a methanol crossover model in DMFC applications

A design of experiments (DOEs) coupled with a mathematical model was used to quantify the factors affecting methanol crossover in a direct methanol fuel cell (DMFC). The design of experiments examined the effects of temperature, cathode stoichiometry, anode methanol flow rate, clamping force, anode catalyst loading, cathode catalyst loading (CCL), and membrane thickness as a function of current and it also considered the interaction between any two of these factors. The analysis showed that significant factors affecting methanol crossover were temperature, anode catalyst layer thickness, and methanol concentration. The analysis also showed how these variables influence the total methanol crossover in different ways due to the effects on diffusion of methanol through the membrane, electroosmotic drag, and reaction rate of methanol at the anode and cathode. For example, as expected analysis showed that diffusion was significantly affected by the anode and cathode interfacial concentration, by the thickness of the anode catalyst layer and membrane, and by the diffusion coefficient in the membrane. Less obvious was the decrease in methanol crossover at low cathode flow rates were due to the formation of a methanol film at the membrane/cathode catalyst layer interface. The relative proportions of diffusion and electroosmotic drag in the membrane changed significantly with the cell current of the cell.     

Low methanol crossover and high efficiency direct methanol fuel cell: The influence of diffusion layers

This experimental work aims to investigate the possibility to reduce methanol crossover in DMFC modifying diffusion layer characteristics. Improvements in crossover measurement are firstly proposed, permitting to conclude that in the investigated conditions carbon dioxide flow through the membrane can be neglected. The experimental results evidence that introducing appropriate anode and cathode microporous layers determines: a strong reduction in methanol crossover, approximately 45% at low current density; a considerable increment of efficiency; a moderate decrease of power density. The complete experimental analysis demonstrates that methanol transport in both liquid and vapour phases can be controlled modifying properly diffusion layer characteristics in order to increase DMFC efficiency.     

DMFC anode polarization: Experimental analysis and model validation

Anode two-phase flow has an important influence on DMFC performance and methanol crossover. In order to elucidate two-phase flow influence on anode performance, in this work, anode polarization is investigated combining experimental and modelling approach. A systematic experimental analysis of operating conditions influence on anode polarization is presented. Hysteresis due to operating condition is observed; experimental results suggest that it arises from methanol accumulation and has to be considered in evaluating DMFC performances and measurements reproducibility. A model of DMFC anode polarization is presented and utilised as tool to investigate anode two-phase flow. The proposed analysis permits one to produce a confident interpretation of the main involved phenomena. In particular, it confirms that methanol electro-oxidation kinetics is weakly dependent on methanol concentration and that methanol transport in gas phase produces an important contribution in anode feeding. Moreover, it emphasises the possibility to optimise anode flow rate in order to improve DMFC performance and reduce methanol crossover.     

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.     

Modeling of water transport through the membrane electrode assembly for direct methanol fuel cells

In this work, a one-dimensional, isothermal two-phase mass transport model is developed to investigate the water transport through the membrane electrode assembly (MEA) for liquid-feed direct methanol fuel cells (DMFCs). The liquid (methanol–water solution) and gas (carbon dioxide gas, methanol vapor and water vapor) two-phase mass transport in the porous anode and cathode is formulated based on classical multiphase flow theory in porous media. In the anode and cathode catalyst layers, the simultaneous three-phase (liquid and vapor in pores as well as dissolved phase in the electrolyte) water transport is considered and the phase exchange of water is modeled with finite-rate interfacial exchanges between different phases. This model enables quantification of the water flux corresponding to each of the three water transport mechanisms through the membrane for DMFCs, such as diffusion, electro-osmotic drag, and convection. Hence, with this model, the effects of MEA design parameters on water crossover and cell performance under various operating conditions can be numerically investigated.     

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.     

Two-dimensional two-phase mass transport model for methanol and water crossover in air-breathing direct methanol fuel cells

A two-dimensional two-phase mass transport model has been developed to predict methanol and water crossover in a semi-passive direct methanol fuel cell with an air-breathing cathode. The mass transport in the catalyst layer and the discontinuity in liquid saturation at the interface between the diffusion layer and catalyst layer are particularly considered. The modeling results agree well with the experimental data of a home-assembled cell. Further studies on the typical two-phase flow and mass transport distributions including species, pressure and liquid saturation in the membrane electrode assembly are investigated. Finally, the methanol crossover flux, the net water transport coefficient, the water crossover flux, and the total water flux at the cathode as well as their contributors are predicted with the present model. The numerical results indicate that diffusion predominates the methanol crossover at low current densities, while electro-osmosis is the dominator at high current densities. The total water flux at the cathode is originated primarily from the water generated by the oxidation reaction of the permeated methanol at low current densities, while the water crossover flux is the main source of the total water flux at high current densities.     

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.     

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.     

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.     

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.     

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.     

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.     

Mass transport analysis of a passive vapor-feed direct methanol fuel cell

A two-dimensional, two-phase, non-isothermal model using the multi-fluid approach was developed for a passive vapor-feed direct methanol fuel cell (DMFC). The vapor generation through a membrane vaporizer and the vapor transport through a hydrophobic vapor transport layer were both considered in the model. The evaporation/condensation of methanol and water in the diffusion layers and catalyst layers was formulated considering non-equilibrium condition between phases. With this model, the mass transport in the passive vapor-feed DMFC, as well as the effects of various operating parameters and cell configurations on the mass transport and cell performance, were numerically investigated. The results showed that the passive vapor-feed DMFC supplied with concentrated methanol solutions or neat methanol can yield a similar performance with the liquid-feed DMFC fed with much diluted methanol solutions, while also showing a higher system energy density. It was also shown that the mass transport and cell performance of the passive vapor-feed DMFC depend highly on both the open area ratio of the vaporizer and the methanol concentration in the tank.     

New RuO2 and carbon–RuO2 composite diffusion layer for use in direct methanol fuel cells

A RuO₂ diffusion layer is examined for use in direct methanol fuel cells (DMFC) by comparison with acetylene black and Vulcan XC-72R. In the test with a DMFC unit cell, the RuO₂ diffusion layer is superior to the other two materials. The difference in performance is interpreted in terms of structural and electrical properties which are evaluated by porosity, scanning electron microscopy and resistance measurements. The RuO₂ diffusion layer displays different behaviors at the anode and cathode sides. These characteristics can be attributed to a reduced loss of catalyst in the active catalyst layer, which leads to increased methanol diffusion at the anode and prevention of water flooding in the cathode. The effect of the RuO₂ diffusion layer on cell performance becomes more pronounced at lower temperatures and during operation in the presence of air. Finally, a carbon–RuO₂ composite is evaluated as a diffusion layer material for a DMFC.