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.     

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.     

Numerical analysis for a vapor feed miniature direct methanol fuel cell system

A two-dimensional, multiphase model is presented and analyzed for a vapor feed DMFC system. The DMFC model is based on the multiphase mixture formulation and encompasses all components in the porous regions of a vapor feed DMFC using a single computation domain. The evaporation/condensation phenomenon in the anode flow channel is modeled in a separated way. An iterative numerical scheme is used to solve the governing equations in a coupled manner. Numerical simulations are carried out to explore the transient and polarization characteristics of the DMFC, including methanol crossover through the membrane, temperature evolution, anodic and cathodic overpotentials. The results indicate the anode flow channel for the feeding methanol solution is the key parameter for the DMFC performance. The numerical results are also compared with the experimental data with good agreement.     

The mass transport based on convection effects in a passive DMFC under open-circuit conditions

The study investigates the open-circuit characteristics of a passive direct methanol fuel cell (DMFC) based on temperature-induced convection effects, including the reactants distributions at anode, the non-uniform temperature distribution and the methanol crossover. A two-dimensional, well-thought-out numerical model coupling with mass transfer and momentum transfer is exploited for DMFC to investigate its inner component and temperature distributions under open-circuit condition. In addition, a 4.0 cm² passive DMFC has been designed and manufactured by the laser-cutting technology for experimental verification. The average methanol crossover flux, methanol diffusion coefficient and crossover current are obtained, which coincide with the simulation data well. The temperature-induced convection simulation results show that the distorted temperature distribution becomes more obvious with higher methanol concentration. Furthermore, the polarization curve, cell temperature and open-circuit voltage (OCV) are measured by varying the methanol concentration to conduct more in-depth research on DMFC performance at open circuit state. The results indicate that the temperature is increased, whereas the OCV is decreased with the increase of methanol concentration, accompanied by the phenomenon of methanol crossover is aggravated. The paper provides the theory basis and the optimal operating parameters for safe start-up of DMFC.     

Operational characteristics of the direct methanol fuel cell stack on fuel and energy efficiency with performance and stability

This paper is presented to investigate operational characteristics of a direct methanol fuel cell (DMFC) stack with regard to fuel and energy efficiency, including its performance and stability under various operating conditions. Fuel efficiency of the DMFC stack is strongly dependent on fuel concentration, working temperature, current density, and anode channel configuration in the bipolar plates and noticeably increases due to the reduced methanol crossover through the membrane, as the current density increases and the methanol concentration, anode channel depth, and temperature decreases. It is, however, revealed that the energy efficiency of the DMFC stack is not always improved with increased fuel efficiency, since the reduced methanol crossover does not always indicate an increase in the power of the DMFC stack. Further, a lower methanol concentration and temperature sacrifice the power and operational stability of the stack with the large difference of cell voltages, even though the stack shows more than 90% of fuel efficiency in this operating condition. The energy efficiency is therefore a more important characteristic to find optimal operating conditions in the DMFC stack than fuel efficiency based on the methanol utilization and crossover, since it considers both fuel efficiency and cell electrical power. These efforts may contribute to commercialization of the highly efficient DMFC system, through reduction of the loss of energy and fuel.     

Real time measurements of methanol crossover in a DMFC

Methanol crossover is a serious problem in a direct methanol fuel cell (DMFC), which causes significant voltage loss and waste of fuel. Due to methanol crossover, most DMFCs must operate on a fuel with a very low methanol concentration; yet very low methanol concentration also causes a poor cell performance. Thus, it is very important to find the optimal operating conditions of methanol concentration and other operating parameters. In this research, methanol crossover rate in a DMFC is determined by measuring the carbon dioxide concentration at the cathode exit in real time. By measuring methanol crossover and cell performances at different inlet methanol concentrations and various operating conditions three types of characteristics are identified in the relationships between methanol crossover and cell current density. Further analysis of these relationships between methanol crossover and cell performances reveals the optimal methanol concentration and other operating parameters, at which the cell reaches optimal performance without incurring excessive methanol crossover. Furthermore, transient peaks of methanol crossover have been identified when the cell voltage suddenly changes. Analyses of these peaks show that they are caused by the hysteresis of methanol concentration at the interface between the anode catalyst layer and the membrane.     

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

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

Water management in 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.     

A three-dimensional two-phase flow model for a liquid-fed direct methanol fuel cell

A three-dimensional, two-phase, multi-component model has been developed for a liquid-fed DMFC. The modeling domain consists of the membrane, two catalyst layers, two diffusion layers, and two channels. Both liquid and gas phases are considered in the entire anode, including the channel, the diffusion layer and the catalyst layer; while at the cathode, two phases are considered in the gas diffusion layer and the catalyst layer but only single gas phase is considered in the channels. For electrochemical kinetics, the Tafel equation incorporating the effects of two phases is used at both the cathode and anode sides. At the anode side the presence of gas phase reduces the active catalyst areas, while at the cathode side the presence of liquid water reduces the active catalyst areas. The mixed potential effects due to methanol crossover are also included in the model. The results from the two-phase flow mode fit the experimental results better than those from the single-phase model. The modeling results show that the single-phase models over-predict methanol crossover. The modeling results also show that the porosity of the anode diffusion layer plays an important role in the DMFC performance. With low diffusion layer porosity, the produced carbon dioxide cannot be removed effectively from the catalyst layer, thus reducing the active catalyst area as well as blocking methanol from reaching the reaction zone. A similar effect exits in the cathode for the liquid water.     

Modeling and simulation of a direct methanol fuel cell anode

A mathematical model for the anode of a direct methanol fuel cell (DMFC) is presented. This model considers the mass transport in the whole anode compartment and the proton exchange membrane (PEM), together with the kinetic and ohmic resistance effects through the catalyst layer. The influence of key parameters on methanol crossover and anode performance is investigated. Our results indicate that, at low current density and high methanol concentration, the methanol crossover poses a serious problem for a DMFC. The anodic overpotential and reaction-rate distributions throughout the catalyst layer are more sensitive to the protonic conductivity than to the diffusion coefficient of methanol. Increasing the protonic conductivity can effectively enhance the performance of a DMFC.     

A global transient,one-dimensional,two-phase model for direct methanol fuel cells (DMFCs) – Part II: Analysis of the time-dependent thermal behavior of DMFCs

A transient-thermal model based on a lumped system is newly developed and implemented in a one-dimensional (1D), two-phase rigorous direct methanol fuel cell (DMFC) model presented in Part I. In this model, the main focus lies on the investigation of the transient thermal behavior of DMFCs and its influence on methanol crossover, cell performance, and efficiency. 1D simulations are carried out and the time-dependent thermal behaviors of DMFCs are analyzed for various methanol-feed concentrations and external heat-transfer conditions. Predicting the close interactions between the evolution of the transient temperature, methanol crossover, cell voltage, and efficiency during DMFC operations, the simulations of transient behavior indicate that the insufficient cooling of DMFCs finally lead to thermal runaway, particularly under high methanol-feed concentrations. Therefore, it is concluded that an efficient cooling system is greatly needed to safeguard DMFC operations and enhance the performance of DMFCs. The present 1D DMFC model is a useful tool for attaining a better understanding of complicated physical phenomena in DMFCs, which assists in optimizing the operating conditions of such cells and material/design parameters.     

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.     

Non-isothermal dynamic modelling and optimization of a direct methanol fuel cell

A non-isothermal dynamic optimization model of direct methanol fuel cells (DMFCs) is developed to predict their performance with an effective optimum-operating strategy. After investigating the sensitivities of the transient behaviour (the outlet temperature, crossovers of methanol and water, and cell voltage) to operating conditions (the inlet flow rates into anode and cathode compartments, and feed concentration) through dynamic simulations, we find that anode feed concentration has a significantly larger impact on methanol crossover, temperature, and cell voltage than the anode and cathode flow rates. Also, optimum transient conditions to satisfy the desired fuel efficiency are obtained by dynamic optimization. In the developed model, the significant influence of temperature on DMFC behaviour is described in detail with successful estimation of its model parameters.     

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.     

Effect of design and operating parameters on dynamic response of a micro direct methanol fuel cell

Dynamic response of the micro direct methanol fuel cell (μDMFC) is of significant importance, and has to be considered during cell design as well as operation. In order to explore the effect of design parameter and operating conditions on dynamic behavior, a μDMFC with stainless steel current collectors as well as stainless steel mesh was fabricated. Different load conditions were applied to the cell to test the effect of stainless steel mesh, cell orientation, methanol concentration and methanol flow rate on transient performance of the cell. A variety of physical and electrochemical processes in the cell are coupled and interactive, which determine that factors affecting transient behavior are complex. But experimental results indicate that methanol crossover through proton exchange membrane (PEM), methanol transportation in anode, removal of CO₂ bubbles and heat loss brought away by methanol solution are four crucial causes influencing dynamic behavior 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.     

Analysis of the polarization of a direct methanol fuel cell using a pseudo-reversible hydrogen reference electrode

In order to observe the performance of the anode and cathode during actual direct methanol fuel cell (DMFC) operating conditions and to minimize the polarization of the reference electrode, we used a reversible hydrogen reference electrode (RHE) with its instability minimized. For analysis of the I–V polarization curve of each electrode, Tafel plots were used as the diagnostic tool. According to the slopes in the Tafel plot, the I–V polarization curves of each electrode were divided into the several regions. The effects of operating parameters on the performance of each electrode were interpreted in terms of mass transfer and electrode activation. The methanol and oxygen crossover through the membrane significantly affected the performance of the cell.     

Basic model for membrane electrode assembly design for direct methanol fuel cells

This research proposes a model that predicts the effect of the anode diffusion layer and membrane properties on the electrochemical performance and methanol crossover of a direct methanol fuel cell (DMFC) membrane electrode assembly (MEA). It is an easily extensible, lumped DMFC model. Parameters used in this design model are experimentally obtainable, and some of the parameters are indicative of material characteristics. The quantification of these material parameters builds up a material database. Model parameters for various membranes and diffusion layers are determined by using various techniques such as polarization, mass balance, electrochemical impedance spectroscopy (EIS), and interpretation of the response of the cell to step changes in current. Since the investigation techniques cover different response times of the DMFC, processes in the cell such as transport, reaction and charge processes can be investigated separately. Properties of single layers of the MEA are systematically varied, and subsequent analysis enables identification of the influence of the layer's properties on the electrochemical performance and methanol crossover. Finally, a case study indicates that the use of a membrane with lower methanol diffusivity and a thicker anode micro-porous layer (MPL) yields MEAs with lower methanol crossover but similar power density.     

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.     

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.