Mass and heat transport in direct methanol fuel cells

The direct methanol fuel cell (DMFC) is a better alternative to the conventional battery. The DMFC offers several advantages, namely, faster building of potential and longer-lasting fuel, however, there are still several issues that need to be addressed to design a better DMFC system. This article is a wide-ranging review of the most up-to-date studies on mass and heat transfer in the DMFC. The discussion will be focused on the critical problems limiting the performance of DMFCs. In addition, a technique for upgrading the DMFC with an integrated system will be presented, along with existing numerical models for modeling mass and heat transfer as well as cell performance.     

Analyses of mass and heat transport interactions in a direct methanol fuel cell

In this paper, a two-dimensional, two-phase, non-isothermal model is presented to predict the electrochemical, mass transfer and heat transfer behaviors in a direct methanol fuel cell (DMFC). Governing equations including the momentum, continuity, heat transfer, proton and electron transport, species transport for water, methanol, and all the gas species (carbon dioxide, methanol vapor, water vapor, oxygen, and nitrogen) and the auxiliary equations are coupled to studying the various phenomena in DMFC. The modeling results agree well with the four different experimental data in an extensive range of operation conditions. A parametric study is also performed to examine the effects of the cell voltage on the different variables, such as cell temperature, liquid methanol concentration distribution, oxygen concentration distribution, and anode gas pressure distribution. The results show that the cell temperature is highly sensitive to the change in the cell voltage as well as methanol concentration distribution. Moreover, it is found that the cell voltage significantly influences the oxygen concentration distribution and the anode gas pressure distribution.     

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.     

Mass transport phenomena in direct methanol fuel cells

Clean and highly efficient energy production has long been sought to solve energy and environmental problems. Fuel cells, which convert the chemical energies stored in fuel directly into electrical energy, are expected to be a key enabling technology for this century. This article is concerned with one of the most advanced fuel cells – direct methanol fuel cells (DMFCs). We present a comprehensive review of the state-of-the-art studies of mass transport of different species, including the reactants (methanol, oxygen and water) and the products (water and carbon dioxide) in DMFCs. Rather than elaborating on the details of the previous numerical modeling and simulation, the article emphasizes: i) the critical mass-transport issues that need to be addressed so that the performance and operating stability of DMFCs can be upgraded, ii) the basic mechanisms that control the mass-transport behaviors of reactants and products in this type of fuel cell, and iii) the previous experimental and numerical findings regarding the correlation between the mass transport of each species and cell performance.     

Electrode in direct methanol fuel cells

Nanotechnology has recently generated a lot of attention and high expectations not only in the academic community but also among investors, scientists and researchers in both government and industry sectors. Its unique capability to fabricate new structures at the atomic scale has already produced novel materials and devices with great potential applications in a wide number of fields. Up to now, the electrodes in direct methanol fuel cells (DMFCs) have generally been based on the porous carbon gas diffusion electrodes that are employed in proton exchange membrane fuel cells. Typically, the structure of such electrodes is comprised of a catalyst layer and a diffusion layer, the latter being carbon cloth or carbon paper. It is a challenge to develop an electrode with high surface area, good electrical conductivity and suitable porosity to allow good reactant flux and high stability in the fuel cell environment. This paper presents an overview of electrode structure in general and recent material developments, with particular attention paid to the application of nanotechnology in DMFCs.     

Systematic approach for modeling methanol mass transport on the anode side of direct methanol fuel cells

A systematic method for modeling direct methanol fuel cells, with a focus on the anode side of the system, is advanced for the purpose of quantifying the methanol crossover phenomenon and predicting the concentration of methanol in the anode catalyst layer of a direct methanol fuel cell. The model accounts for fundamental mass transfer phenomena at steady state, including convective transport in the anode flow channel, as well as diffusion and electro-osmotic drag transport across the polymer electrolyte membrane. Experimental measurements of methanol crossover current density are used to identify five modeling parameters according to a systematic parameter estimation methodology. A validation study shows that the model matches the experimental data well, and the usefulness of the model is illustrated through the analysis of effects such as the choice fuel flow rate in the anode flow channel and the presence of carbon-dioxide bubbles.     

Current density measurements in direct methanol fuel cells

The current density in the fuel cell is the direct consequence of reactions taking place over the active surface area. Thus, measurement of its distribution will lead to identification of the location and nature of reactions and will give opportunity to improve the overall efficiency of fuel cells. Within this study, the current density distribution in a direct methanol fuel cell was analyzed by segmenting the current collector into nine sections. Besides, the effect of the different operating parameters such as molarity, flow rate and reactant gas on the current density distribution was analyzed.     

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 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.     

An effective layout of polyaniline nanofibers incorporated in membrane-electrode assembly as methanol transport regulator for direct methanol fuel cells

This study reports a novel strategy by using polyaniline nanofibers (PANFs) to modify membrane-electrode assembly (MEA) for improving direct methanol fuel cell (DMFC) performance. First of all, a series of PANFs emeraldine salt was synthesized and characterized. Then, we investigated the effect of PANFs layout in MEA on DMFC performance. Three different placements to incorporate the as-synthesized PANFs in anodes include (1) placing a layer of PANFs between catalyst layer (CL) and proton exchange membrane (PEM), (2) mixing with catalyst slurry and coating onto gas diffusion layer (GDL), and (3) placing a layer of PANFs between CL and GDL. Polarization curves indicate that the third method is superior to the others and is adopted as the incorporation layout thereafter. Both methanol transport resistance and methanol crossover of the PANFs-modified MEA are studied further. The DMFC incorporated with H₂SO₄-doped PANFs obtained after the re-doping process with 2 mol L⁻¹ H₂SO₄ performs a power density as high as 53 mW cm⁻², about 20% higher than that of the pristine one without PANFs incorporation. However, an excessive doping level may result in a higher methanol transport resistance due to PANFs aggregation and thus deteriorate DMFC performance. This study provides a simple and effective way by placing a layer of PANFs between CL and GDL in anode to act as methanol transport regulator and improve DMFC performance consequently.     

Study on water transport in PEM of a direct methanol fuel cell

Water transport phenomenon in PEM and the mechanism of occurrence and development of a two-phase countercurrent flow with corresponding transport phenomenon in the PEM are analyzed. A one-dimensional steady state model of heat and mass transfer in porous media system with internal volumetric ohmic heating is developed and simulated numerically. The results show that two dimensionless parameters D and N, which reflect the liquid water flow rate and inner heat source in the PEM, respectively, are the most important factors for the water fraction and thermal balance in the PEM. The saturation profiles within the two-phase region at various operating modes are obtained. Smaller mass flow rate of liquid water and high current density are the major contributions to the membrane dehydration.     

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 algorithm for sensor-less fuel control of direct methanol fuel cells

We report an algorithm for real-time control of the fuel of a DMFC. The MEA voltage decay coefficients [e₁, e₂], and I-V-T, M′-I-T, and W′-I-T curves (where I is the current, V the voltage, T the temperature, and M′ and W′ the methanol and water consumption rates, respectively) of n fuels with specified methanol concentrations C_M,k (k = 1, 2,…, n) are pre-established and form (I,V,T), (M′,I,T), and (W′,I,T) surfaces for each C_M,k. The in situ measured (I,V,T)_u after voltage decay correction is applied to the n preset (I,V,T) surfaces to estimate C_M,u (the C_M corresponding to (I,V,T)_u) using an interpolation procedure. The C_M,u is then applied to the n preset (M′,I,T) and (W′,I,T) surfaces to estimate cumulated “methanol” and “water” consumed quantities . Thus in a real-time system, the C_M and total quantity of fuel can be controlled using the estimated C_M,u and cumulated “methanol” and “water” consumed quantities.     

Compact direct methanol fuel cells for portable application

Consumers’ demand for portable audio/video/ICT products has driven the development of advanced power technologies in recent years. Fuel cells are a clean technology with low emissions levels, suitable for operation with renewable fuels and capable, in a next future, of replacing conventional power systems meeting the targets of the Kyoto Protocol for a society based on sustainable energy systems. Within such a perspective, the objective of the European project MOREPOWER (compact direct methanol fuel cells for portable applications) is the development of a low-cost, low temperature, portable direct methanol fuel cell (DMFC; nominal power 250 W) with compact construction and modular design for the potential market area of weather stations, medical devices, signal units, gas sensors and security cameras. This investigation is focused on a conceptual study of the DMFC system carried out in the Matlab/Simulink^® platform: the proposed scheme arrangements lead to a simple equipment architecture and a efficient process.     

Passive direct methanol fuel cells for portable electronic devices

Due to the increasing demand for electricity, clean, renewable energy resources must be developed. Thus, the objective of the present study was to develop a passive direct methanol fuel cell (DMFC) for portable electronic devices. The power output of six dual DMFCs connected in series with an active area of 4 cm² was approximately 600 mW, and the power density of the DMFCs was 25 mW cm⁻². The DMFCs were evaluated as a power source for mobile phone chargers and media players. The results indicated that the open circuit voltage of the DMFC was between 6.0 V and 6.5 V, and the voltage under operating conditions was 4.0 V. The fuel cell was tested on a variety of cell phone chargers, media players and PDAs. The cost of energy consumption by the proposed DMFC was estimated to be USD 20 W⁻¹, and the cost of methanol is USD 4 kW h. Alternatively, the local conventional electricity tariff is USD 2 kW h. However, for the large-scale production of electronic devices, the cost of methanol will be significantly lower. Moreover, the electricity tariff is expected to increase due to the constraints of fossil fuel resources and pollution. As a result, DMFCs will become competitive with conventional power sources.     

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.     

Towards operating direct methanol fuel cells with highly concentrated fuel

A significant advantage of direct methanol fuel cells (DMFCs) is the high specific energy of the liquid fuel, making it particularly suitable for portable and mobile applications. Nevertheless, conventional DMFCs have to be operated with excessively diluted methanol solutions to limit methanol crossover and the detrimental consequences. Operation with diluted methanol solutions significantly reduces the specific energy of the power pack and thereby prevents it from competing with advanced batteries. In view of this fact, there exists a need to improve conventional DMFC system designs, including membrane electrode assemblies and the subsystems for supplying/removing reactants/products, so that both the cell performance and the specific energy can be simultaneously maximized. This article provides a comprehensive review of past efforts on the optimization of DMFC systems that operate with concentrated methanol. Based on the discussion of the key issues associated with transport of the reactants/products, the strategies to manage the supply/removal of the reactants/products in DMFC operating with highly concentrated methanol are identified. With these strategies, the possible approaches to achieving the goal of concentrated fuel operation are then proposed. Past efforts in the management of the reactants/products for implementing each of the approaches are also summarized and reviewed.     

Testing of carbon supported Pd-Pt electrocatalysts for methanol electrooxidation in direct methanol fuel cells

In the present work, a detailed characterization of the electrochemical behavior of carbon supported Pd-Pt electrocatalysts toward CO and methanol electrooxidation in direct methanol fuel cells is reported. Technical electrodes containing an ionomer in their catalyst layer were prepared for this purpose. CO and methanol electrooxidation reactions were used as test reactions to compare the electrocatalytic behavior of bimetallic supported nanoparticles in acidic liquid electrolyte and in solid polymer electrolyte (real fuel cell operating conditions). Experimental results in both environments are consistent and show that the electrochemical behavior of carbon supported Pd-Pt depends on their composition, giving the best performance in direct methanol single fuel cell with a Pd:Pt atomic ratio of 25:75 in the catalyst.     

Study of pulsed-current loading of direct methanol fuel cells using a new time-domain model based on bi-functional methanol oxidation kinetics

This work describes a non-linear time-domain model of a direct methanol fuel cell (DMFC) and uses that model to show that pulsed-current loading of a direct methanol fuel cell does not improve average efficiency. Unlike previous system level models, the one presented here is capable of predicting the step response of the fuel cell over its entire voltage range. This improved model is based on bi-functional methanol oxidation reaction kinetics and is derived from a lumped, four-step reaction mechanism. In total, six states are incorporated into the model: three states for intermediate surface adsorbates on the anode electrode, two states for the anode and cathode potentials, and one state for the liquid methanol concentration in the anode compartment. Model parameters were identified using experimental data from a real DMFC. The model was applied to study the steady-state and transient performance of a DMFC with the objective to understand the possibility of improving the efficiency of the DMFC by using periodic current pulses to drive adsorbed CO from the anode catalyst. Our results indicate that the pulsed-current method does indeed boost the average potential of the DMFC by 40 mV; but on the other hand, executing that strategy reduces the overall operating efficiency and does not yield any net benefit.     

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.