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.     

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.     

Two-dimensional two-phase thermal model for passive direct methanol fuel cells

A two-dimensional two-phase thermal model is presented for direct methanol fuel cells (DMFC), in which the fuel and oxidant are fed in a passive manner. The inherently coupled heat and mass transport, along with the electrochemical reactions occurring in the passive DMFC is modeled based on the unsaturated flow theory in porous media. The model is solved numerically using a home-written computer code to investigate the effects of various operating and geometric design parameters, including methanol concentration as well as the open ratio and channel and rib width of the current collectors, on cell performance. The numerical results show that the cell performance increases with increasing methanol concentration from 1.0 to 4.0 M, due primarily to the increased operating temperature resulting from the exothermic reaction between the permeated methanol and oxygen on the cathode and the increased mass transfer rate of methanol. It is also shown that the cell performance upgrades with increasing the open ratio and with decreasing the rib width as the result of the increased mass transfer rate on both the anode and cathode.     

Unsteady-state modelling for a passive liquid-feed DMFC

An unsteady-state model was developed for a liquid-feed Direct Methanol Fuel Cell (DMFC) delivery considering two-phase system. The model considered the mass and heat transport in the feed delivery system attached to the anode and cathode of the fuel cell. The results were then compared with the experimental data from in-house fabricated DMFC and steady-state model. It was observed that the unsteady-state model gave more similar results with experimental data then the steady-state model. The effects of feed methanol concentration in the reservoir and current density on mass transport to the catalyst layer were revealed.     

Modeling of dynamic operating behaviors in a liquid-feed direct methanol fuel cell

A transient, two-dimensional two-phase mass transport model is applied to investigate the cell dynamic operating behaviors of a liquid-feed direct methanol fuel cell (DMFC). The influences of various processes on the cell dynamics in response to sudden change of cell current density, methanol feed concentration, oxygen feed concentration, and the transient gas-slug blocking in the anode channel are studied. The results reveal that in response to the sudden drop of cell current density and methanol concentration, the cell voltage exhibits overshooting behavior as a result of the interaction between cathode and anode overpotentials with different time responses. The dominant factor causing the long response of cell voltages is the methanol rebalance in the membrane electrode assembly, which usually takes tens of seconds because of the sluggish methanol transport process. Also, it is indicated that in response to temporary blocking of anode diffusion layer surface with gas slug, the cell can still operate normally for a while because the anode diffusion layer serves as the fuel reservoir. It takes over a minute for the cell to break down in this case studied, implying that the cell output can be maintained stable if the gas bubbles or slugs in the anode channel can be removed quickly. However, too long residence time of gas slug in the channel definitely degrades the cell performance.     

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.     

Analysis of heat and mass transport in a miniature passive and semi passive liquid-feed direct methanol fuel cell

A two-dimensional, transient, multi-phase, multi-component, and non-isothermal model has been developed to solve the heat and mass transport in a passive and semi passive liquid-feed direct methanol fuel cell (DMFC). A semi passive DMFC uses channel at the cathode side to facilitate the oxidant transport. The transient characteristics of the temperature, methanol concentration, methanol crossover, useful current density and methanol evaporation are investigated. The results indicate that the temperature in the fuel cell increases during operation as much as 10 °C, due to the heat generation by internal phase change and the electrochemical reactions. However, it is revealed that the temperature distribution is nearly uniform at any time through all porous layers including the fuel cell and fuel delivery system. The effect of using an active feeding system in the cathode and passive methanol feeding in the anode (semi passive system) on the performance of a fuel cell is also studied. The active oxidant feeding to the cathode catalyst layer in the semi passive cell improved the fuel cell performance compared to that in a passive one. However, in general, the performance of passive cell is better than that in a semi passive one because of more temperature increase in the passive system.     

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.     

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 impedance study of an operating direct methanol fuel cell

An electrochemical impedance spectroscopy (EIS) technique was developed to characterize a direct methanol fuel cell (DMFC) under various operating conditions. A silver/silver chloride electrode was used as an external reference electrode to probe the anode and cathode during fuel cell operation and the results were compared to the conventional anode or cathode half-cell performance measurement using a hydrogen electrode as both the counter and reference electrode. The external reference was sensitive to the anode and the cathode as current was passed in a working DMFC. The impedance spectra and DMFC polarization curves were systematically investigated as a function of air and methanol flow rates, methanol concentration, temperature, and current density. Water flooding in the cathode was also examined.     

Modelling and analysis of a direct methanol fuel cell with under-rib mass transport and two-phase flow at the anode

For the past decade, extensive mathematical modelling has been conducted on the design and optimization of liquid-feed direct methanol fuel cells (DMFCs). Detailed modelling of DMFC operations reveals that a two-phase flow phenomenon at the anode and under-rib convection due to the pressure difference between the adjacent channels both contribute significantly to mass-transfer in a DMFC and its output performance. In practice, comprehensive simulations based on the finite volume technique for two-phase flow require a high level of numerical complexity in computation. This study presents a complexity-reduced mathematical model that is developed to cover both phenomena for a realistic, but fast, in computation for the prediction and analysis of a DMFC prototype design. The simulation results are validated against experimental data with good agreement. Analysis of the DMFC mass-transfer is made to investigate methanol distribution at anode and its crossover through the proton-exchange membrane. From a comparison of the influence of two-phase flow and under-rib mass-transfer on DMFC performance, the significance of gas-phase methanol transport is established. Simulation results suggest that both the optimization of the flow-field structure and the fuel cell operating parameters (flow rate, methanol concentration and operating temperature) are important factors for competitive DMFC performance output.     

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.     

Two-phase hydrodynamics in a miniature direct methanol fuel cell

We present controlled experiments on a miniature direct methanol fuel cell (DMFC) to study the effects of methanol flow rate, current density, and void fraction on pressure drop across the DMFC anode. We also present an experimental technique to measure void fraction, liquid slug length, and velocity of the two-phase slug flow exiting the DMFC. For our channel geometry in which the diameter of the largest inscribed sphere (a) is 500 μm, pressure drop scales with the number of gas slugs in the channel, surface tension, and a. This scaling demonstrates the importance of capillary forces in determining the hydrodynamic characteristics of the DMFC anode. This work is aimed at aiding the design of fuel pumps and anode flow channels for miniature DMFC systems.     

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.     

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.     

Development of an advanced MEA to use high-concentration methanol fuel in a direct methanol fuel cell system

Despite serious methanol crossover issues in Direct Methanol Fuel Cells (DMFCs), the use of high-concentration methanol fuel is highly demanded to improve the energy density of passive fuel DMFC systems for portable applications. In this paper, the effects of a hydrophobic anode micro-porous layer (MPL) and cathode air humidification are experimentally studied as a function of the methanol-feed concentration. It is found in polarization tests that the anode MPL dramatically influences cell performance, positively under high-concentration methanol-feed but negatively under low-concentration methanol-feed, which indicates that methanol transport in the anode is considerably altered by the presence of the anode MPL. In addition, the experimental data show that cathode air humidification has a beneficial effect on cell performance due to the enhanced backflow of water from the cathode to the anode and the subsequent dilution of the methanol concentration in the anode catalyst layer. Using an advanced membrane electrode assembly (MEA) with the anode MPL and cathode air humidification, we report that the maximum power density of 78 mW/cm² is achieved at a methanol-feed concentration of 8 M and cell operating temperature of 60 °C. This paper illustrates that the anode MPL and cathode air humidification are key factors to successfully operate a DMFC with high-concentration methanol fuel.     

A study on the overall efficiency of direct methanol fuel cell by methanol crossover current

This paper was presented to determine the methanol crossover and efficiency of a direct methanol fuel cell (DMFC) under various operating conditions such as cell temperature, methanol concentration, methanol flow rate, cathode flow rate, and cathode backpressure. The methanol crossover measurements were performed by measuring crossover current density at an open circuit using humidified nitrogen instead of air at the cathode and applied voltage with a power supply. The membrane electrode assembly (MEA) with an active area of 5 cm² was composed of a Nafion 117 membrane, a Pt–Ru (4 mg/cm²) anode catalyst, and a Pt (4 mg/cm²) cathode catalyst. It was shown that methanol crossover increased by increasing cell temperature, methanol concentration, methanol flow rate, cathode flow rate and decreasing cathode backpressure. Also, it was revealed that the efficiency of the DMFC was closely related with methanol crossover, and significantly improved as the cell temperature and cathode backpressure increased and methanol concentration decreased.     

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.     

Characterization of direct methanol fuel cells by ac impedance spectroscopy

The processes taking place in direct methanol fuel cells (DMFC) are characterized by ac impedance spectroscopy under realistic operating conditions. This method allows the separate examination of anode kinetics, anode mass transport, cathode kinetics, cathode mass transport, and membrane conductivity, making it a valuable diagnostic tool for DMFC development.     

A 3D model for the free-breathing direct methanol fuel cell: Methanol crossover aspects and validations with current distribution measurements

A three-dimensional model has been developed for the free-breathing direct methanol fuel cell (DMFC) assuming steady-state isothermal and single-phase conditions. Especially the MeOH crossover phenomenon is investigated and the model validations are done using previous cathodic current distribution measurements. A free convection of air is modelled in the cathode channels and diffusion and convection of liquid (anode) and gaseous species (cathode) in the porous transport layers. The MeOH flow in the membrane is described with diffusion and protonic drag. The parameter ψ$\psi$ in the model describes the MeOH oxidation rate at the cathode and it is fitted according to the measured current distributions. The model describes the behaviour of the free-breathing DMFC, when different operating parameters such as cell temperature, MeOH concentration and flow rate are varied in a wide range. The model also predicts the existence of the experimentally observed electrolytic domains, i.e. local regions of negative current densities. Altogether, the developed model is in reasonable agreement with both the measured current distributions and polarization curves. The spatial information gained of mass transfer phenomena inside the DMFC is valuable for the optimization of the DMFC operating parameters.