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.     

Passive direct methanol fuel cells fed with methanol vapor

A vapor fed passive direct methanol fuel cell (DMFC) is proposed to achieve a high energy density by using pure methanol for mobile applications. Vapor is provided from a methanol reservoir to the membrane electrode assembly (MEA) through a vaporizer, barrier and buffer layer. With a composite membrane of lower methanol cross-over and diffusion layers of hydrophilic nanomaterials, the humidity of the MEA was enhanced by water back diffusion from the cathode to the anode through the membrane in these passive DMFCs. The humidity in the MEA due to water back diffusion results in the supply of water for an anodic electrochemical reaction with a low membrane resistance. The vapor fed passive DMFC with humidified MEA maintained 20–25 mW cm⁻² power density for 360 h and performed with a 70% higher fuel efficiency and 1.5 times higher energy density when compared with a liquid fed passive DMFC.     

Improving the water management and cell performance for the passive vapor-feed DMFC fed with neat methanol

A passive vapor-feed direct methanol fuel cell (DMFC) was experimentally investigated to improve its water management and cell performance when neat methanol was directly used. The effects of different water management approaches, including the addition of a water management layer (WML) and a hydrophobic air filter layer (AFL), and the use of thinner membrane on the cell performance, internal resistance, and fuel efficiency were investigated. The transient discharging behavior and long-term stability of the passive vapor-feed DMFC with the optimized water management were also studied. The results showed that by adding a WML and an AFL, or thinning the membrane thickness, the water management capability can be highly improved, not only enhancing the water recovery from the cathode to the anode, leading to a lower internal resistance and better cell performance, but also curbing the methanol crossover, increasing the fuel efficiency. It is also seen from the long-term constant-voltage test that the discharged current varied with the methanol concentration in the tank and the ambient temperature, while no evident permanent performance degradation was encountered after the 150 h test.     

Small direct methanol fuel cells with passive supply of reactants

Small, stand-alone, direct methanol fuel cells (DMFCs) that have no auxiliary liquid pumps and gas blowers/compressors are known as passive DMFCs. The devices are ideal for powering portable electronic devices, as this type of fuel cell uniquely has a simple and compact system and no parasitic power losses. This article provides a comprehensive review of experimental and numerical studies of heat and mass transport in passive DMFCs. Emphasis is placed on the mechanisms and key issues of the mass transport of each species through the fuel cell structure under the influence of passive forces. It is shown that the key issue regarding the methanol supply is how to feed high-concentration methanol solution but with minimum methanol crossover through the membrane so that both the system specific energy and cell performance can be maximized. The key issue regarding the oxygen supply is how to enhance the removal of liquid water from the cathode under the air-breathing condition. For water transport, the aim is to transport the water produced on the cathode through the membrane to the anode by optimizing the design of the membrane electrode assembly so that the fuel cell can be operated with pure methanol and with minimum flooding at the cathode. The heat loss from a passive DMFC is usually large and it is therefore critically important to reduce this feature so that the fuel cell can be operated at a sufficiently high temperature, which critically affects the cell performance.     

Start-up and steady-state operation of a passive vapor-feed direct methanol fuel cell fed with pure methanol

A transient, two-dimensional, two-phase, multi-component, non-isothermal model is developed to investigate the start-up and steady-state characteristics of a fully passive, vapor-feed direct methanol fuel cell fed with pure methanol. The model considers the species, heat, charge and electrolyte-dissolved water transport in a single computational domain. During the steady-state operation, methanol loss due to evaporation from the cell to the ambient decreases with an increasing current density. Both the scale analysis and the predictions from the full numerical model reveal that the transient response time depends primarily on the cell load. At high current densities, mass consumption in the anode catalyst layer becomes dominant in the cell transient response time, whereas for the lower current densities, both the diffusive liquid transport in the anode and the mass consumption in the anode catalyst layers are predominant.     

Effect of the cathode open ratios on the water management of a passive vapor-feed direct methanol fuel cell fed with neat methanol

A novel approach has been proposed to improve the water management of a passive direct methanol fuel cell (DMFC) fed with neat methanol without increasing its volume or weight. By adopting perforated covers with different open ratios at the cathode, the water management has been significantly improved in a DMFC fed with neat methanol. An optimized cathode open ratio could ensure both the sufficient supply of oxygen and low water loss. While changing the open ratio of anode vaporizer can adjust the methanol crossover rate in a DMFC. Furthermore, the gas mixing layer, added between the anode vaporizer and the anode current collector to increase the mass transfer resistance, can improve the cell performance, decrease the methanol crossover, and increase the fuel efficiency. For the case of a DMFC fed with neat methanol, an anode vaporizer with the open ratio of 12% and a cathode open ratio of 20% produced the highest peak power density, 22.7 mW cm⁻², and high fuel efficiency, 70.1%, at room temperature of 25 ± 1 °C and ambient humidity of 25-50%.     

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.     

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.     

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.     

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.     

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.     

One-dimensional and non-isothermal model for a passive DMFC

Passive direct methanol fuel cells (DMFCs) are promising energy sources for portable electronic devices. Different from DMFCs with active fuel feeding systems, passive DMFCs with nearly stagnant fuel and air tend to bear comparatively less power densities. A steady state, one-dimensional, multi-component and thermal model is described and applied to simulate the operation of a passive direct methanol fuel cell. The model takes into consideration the thermal and mass transfer effects, along with the electrochemical reactions occurring in the passive DMFC. The model can be used to predict the methanol, oxygen and water concentration profiles in the anode, cathode and membrane as well as to estimate the methanol and water crossover and the temperature profile across the cell. Polarization curves are numerically simulated and successfully compared with experiments for different methanol feed concentrations. The model predicts with accuracy the influence of the methanol feed concentration on the cell performance and the correct trends of the current density and methanol feed concentration, on methanol and water crossover. The model is rapidly implemented and is therefore suitable for inclusion in real-time system level DMFC calculations. Due to its simplicity the model can be used to help seek for possibilities of optimizing the cell performance of a passive DMFC by studying impacts from variations of the design parameters such as membrane thickness, catalyst loading, diffusion layers type and thicknesses.     

Effect of black catalyst ionomer content on the performance of passive DMFC

The effect of the ionomer content in the catalyst layers of both the anode and the cathode with the black catalyst on the performance of a passive DMFC was investigated in order to increase the power output of the passive DMFC. In situ cyclic voltammetry has been carried out to evaluate the electrochemically active surface area, ECSA and the catalyst utilization. Under the passive conditions, ionomer content had a significant effect on both the mass transport and the ECSA. The optimum ionomer content was affected by the operating current density whether at anode or at cathode. Under low current density region, i.e., activation over voltage region, 20 wt.% showed the highest performance at the anode and the cathode, and the cell performance in this region was varied in accordance with the results of the ECSA. Under high current density region, i.e., mass transport over voltage region, lower ionomer content, 10 and 15 wt.%, had the highest cell performance at the anode and the cathode, respectively. The decrease in the optimum ionomer content at high current density was related to the low mass transport of methanol at the anode, and the flooding at the cathode at the high ionomer contents. The optimum ionomer content whether at anode or at cathode was 20 wt.%, from the power density point of view. The catalyst utilization was 10% and 25% at optimum conditions at the cathode and the anode respectively.     

A transient, multi-phase and multi-component model of a new passive DMFC

A 2-dimensional, transient multi-phase, multi-component fuel cell model is developed to model a passive fuel delivery system including the fuel cell itself for a direct methanol fuel cell (DMFC). This model captures evaporative effects, as water and fuel management are crucial issues. The evaporation/condensation rates are formulated in a manner to capture non-equilibrium effects between the phases. Also, the full kinetics are modeled at both the anode and cathode catalyst layers, along with the electric potential of the membrane, catalyst and gas diffusion layers. The fuel cell operation is examined by quantifying the fuel consumption due to chemical reaction and evaporation as a function of feed concentration. The passive delivery system utilizes a porous media to passively deliver methanol to the fuel cell while controlling the concentration of methanol at the anode side to limit the amount of methanol cross-over. The results illustrate the feasibility of the passive thermal-management system, and characterize the relevant transport phenomena.     

Vertical operation of passive direct methanol fuel cell employing a porous carbon plate

Vertical operation of a passive DMFC employing a porous carbon plate, PCP, with different resistances for fluid flow and bubble point pressure was investigated to clarify the properties required for the PCP for vertical operation. Moreover, the cell performance was investigated under different solution head pressures within 22 mm height and was discussed based on the methanol transport through the PCP. In contrast to the horizontal orientation, the static pressure of the liquid as a function of its height on the vertical axis h along the PCP surface, in the vertical orientation, enhanced the convective methanol flux through the PCP and affected the DMFC performance depending on the properties of the PCP and the methanol concentration used. The effect of the solution head pressure on the DMFC performance in the vertical orientation could be controlled by using PCP with high bubble point pressures. The DMFC could attain stable performance under both horizontal and vertical cell orientations and different solution head pressures even with 100% methanol by using a PCP with the proper resistance for the methanol transport and bubble point pressure. A thin PCP of 0.5 mm thickness with the proper resistance enabled the vertical operation producing a constant power density over 40 mW/cm² using 100% methanol at 0.25 V.     

Two-phase flow modeling of liquid-feed direct methanol fuel cell

A two-phase flow model was developed for liquid-feed methanol fuel cells (DMFC) to evaluate the effects of various operating parameters on the DMFC performance. In this study, a general homogenous two-dimensional model is described in details for both porous layers and fluid channels. This two-dimensional general model accounts for fluid flow, electrochemical kinetics, current density distribution, hydrodynamics, multi-component transport, and methanol crossover. It starts from basic transport equations including mass conservation, momentum transport, energy balance, and species concentration conservation in different elements of the fuel cell sandwich, as well as the equations for the phase potential in the membrane and the catalyst layers. These governing equations are coupled with chemical reaction kinetics by introducing various source terms. It is found that all these equations are in a very similar form except the source terms. Based on this observation, all the governing equations can be solved using the same numerical formulation in the single domain without prescribing the boundary conditions at the various interfaces between the different elements of the fuel cell. The numerical simulation results, such as velocity field, local current density distribution, and species concentration variation along the flow channel, under various operation conditions are computed. The performance of the DMFC affected by various parameters such as temperature, pressure, and methanol concentration is investigated in this paper. The numerical results are further validated with available experimental data from the published literatures.     

Analysis of the diffusive mass transport in the anode side porous backing layer of a direct methanol fuel cell

In this work we present an analysis of the mass transport in the anode side porous backing layer of a direct methanol fuel cell (DMFC). The effective transport coefficient of different backing layers at various compressions was measured and compared to two different literature models and a single particle random walk simulation which accounts for details of the geometrical fibre microstructure. Based on the measured values of the effective transport coefficient limiting current densities for diffusive transport were calculated taking into account geometric boundary conditions and anisotropic and inhomogeneous backing layer properties. Comparison with the measured values for the limiting current in fuel cell operation shows qualitative agreement. A systematic underestimation indicates that also other transport processes contribute significantly to the mass transfer at the used experimental setup.     

Effect of anode current collector on the performance of passive direct methanol fuel cells

The effect of anode current collector on the performance of passive direct methanol fuel cell (DMFC) was investigated in this paper. The results revealed that the anode of passive DMFC with perforated current collector was poor at removing the produced CO₂ bubbles that blocked the access of fuel to the active sites and thus degraded the cell performance. Moreover, the performances of the passive DMFCs with different parallel current collectors and different methanol concentrations at different temperatures were also tested and compared. The results indicated that the anode parallel current collector with a larger open ratio exhibited the best performance at higher temperatures and lower methanol solution concentrations due to enhanced mass transfer of methanol from the methanol solution reservoir to the gas diffusion layer. However, the passive DMFC with a smaller open ratio of the parallel current collector exhibited the best performance at lower temperatures and higher methanol solution concentrations due to the lower methanol crossover rate. Copyright © 2009 John Wiley & Sons, Ltd.     

Influence of cathode oxygen transport on the discharging time of passive DMFC

In this paper, the long-term discharge performances of passive DMFC at different currents with different cell orientations were investigated. Water produced in the cathode was observed from the photographs taken by a digital camera. The results revealed that the passive DMFC with anode facing upward showed the best long-term discharge performance at high current. A few independent water droplets accumulated in cathode when the anode faced upward. Instead, in the passive DMFC with vertical orientation, a large amount of produced water flowed down along the surface of current collector. The passive DMFC with vertical orientation showed relatively good performance at low current. It was concluded that the cathode produced less water in a certain period of time at smaller current. In addition, the rate of methanol crossover in the passive DMFC with anode facing upward was relatively high, which leaded to a more rapid decrease of the methanol concentration in anode. The passive DMFC with anode facing downward resulted in the worst performance because it was very difficult to remove CO₂ bubbles produced in the anode.     

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.