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.     

Mass spectroscopy for the anode gas layer in a semi-passive DMFC using porous carbon plate Part I: Relationship between the gas composition and the current density

In situ mass spectroscopy with a capillary probe was conducted for the anode gas layer of a semi-passive direct methanol fuel cell (DMFC) employing a porous carbon plate (PCP) in order to evaluate the gas composition in contact with the anode. Different types of PCPs were used for the DMFC, and then the relationship between the gas composition in the gas layer and the current density was investigated. The profiles of the CO₂ gas pressure, methanol and water vapor pressures were discussed on the basis of the current density and the resistance for the methanol and CO₂ transport through the PCP. The current density linearly and identically increased with the increase in the partial pressure of methanol, P_CH3OH, in the gas layer up to 7.5 kPa irrespective of the type of the PCP suggesting that the current was a function of P_CH3OH and it was rate limited by the methanol transport to the anode. The calculated liquid methanol concentration equivalent to the measured gas mixture in the gas layer was about 5–7 M in the optimum conditions. This confirmed that the actual methanol activity on the anode of the DMFC with the PCP was controlled by the PCP and was similar to that of the usual liquid feed DMFC even when a very high concentration of methanol was in the reservoir.     

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.     

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.     

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.     

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.     

The degree and effect of methanol crossover in the direct methanol fuel cell

A simple model is presented to describe the permeation of methanol from the anode to the cathode in direct methanol fuel cell (DMFC). Measured permeation rates of water and methanol through Nafion^® 117 under varied pressure differentials across the membrane are used to determine key parameters in the model. This model is able to explain the effect of oxygen pressure at the cathode and methanol concentration at the anode on the measured cell voltage-current response of the DMFC.     

Mass spectroscopy for the anode gas layer in a semi-passive direct methanol fuel cell using porous carbon plate: Part II. Relationship between the reaction products and the methanol and water vapor pressures

Subsequent to Part I, in situ mass spectrometry using a capillary probe was conducted in order to evaluate the gas condition of the anode gas layer of a semi-passive direct methanol fuel cell (DMFC) employing a porous carbon plate (PCP). Different types of PCPs were used for the DMFC, and the production of intermediates besides CO₂, i.e., methylformate (HCOOCH₃), formaldehyde (HCHO) and formic acid (HCOOH), were investigated. The profiles of the vapor pressures of these products were related to the vapor pressure of methanol and water in the gas layer. The production rate of each intermediate was formulated as a power function of the methanol and water vapor pressure ratio, P_CH3OH/P_H2O, with the power factors of 2.07, 0.47 and −0.57 for methylformate, formaldehyde and formic acid, respectively. Based on these equations of the production rates, the product distribution could be quantitatively estimated.     

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.     

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.     

Operational condition analysis for vapor-fed direct methanol fuel cells

This paper investigates the analysis and design of optimal operational conditions for vapor-fed direct methanol fuel cells (DMFCs). Methanol vapor at a temperature of 35 °C is carried with nitrogen gas together with water vapor at 75 °C. In this experimental condition, stoichiometry of 10 is maintained for each fuel gas. The results show that the optimal operational concentration was 25–30 wt.% under methanol vapor feeding at the anode. The peak power was 14 mW cm² in polarization curves. To analyze major losses, the activation losses of the anode and cathode were measured by an in situ reference electrode and a working electrode. The activation loss of the anode is proportional to the water content and the high methanol concentration caused the activation loss of the cathode to increase due to methanol crossover. In the vapor-fed DMFC, the activation loss of the anode is higher than that of the cathode. Also, depending on the variation of the methanol concentration, the IR loss and Faradaic impedance is measured via impedance analysis. The methanol concentration significantly affects the IR loss and kinetics. Although the IR loss was more than the desired value at the optimal condition (25–30 wt.%), it did not significantly affect the cell’s performance. The cell operated at room temperature and ambient pressure that is a typical operation environment of air-breathing fuel cells.     

Transient modeling and analysis of a passive liquid-feed DMFC

A two-dimensional, transient, multi-phase, multi-component model has been developed for a liquid-feed DMFC delivery system including the fuel cell itself. The model considers the mass transport in the feed delivery system attached to the anode inlet of the fuel cell, and the effect of coupled heat and mass transfer under ambient conditions. The results are compared with the existing experimental data with a high level of agreement. The effects of feed methanol concentration in the reservoir and current density on mass transport and performance of DMFC system are revealed. When initial feed concentration in the reservoir decreases, methanol crossover is minimized, but the duration of cell performance is shortened and fuel cell temperature decreases. The anodic overpotential and its increasing rate become higher, while the decreasing rates of solution leftover and methanol concentration in the reservoir become lower. When current density increases, the duration of the cell performance is shortened. While the anodic overpotential and its increasing rate, cell temperature, decreasing rates of methanol crossover, solution leftover and methanol concentration in the reservoir increase.     

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.     

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%.     

Effect of the cathode gas diffusion layer on the water transport behavior and the performance of passive direct methanol fuel cells operating with neat methanol

The passive operation of a direct methanol fuel cell with neat methanol requires the water that is produced at the cathode to diffuse through the membrane to the anode to compensate the methanol oxidation reaction (MOR). Hence, the anode performance of this type of fuel cell can be limited by the water transport rate from the cathode to the anode. In this work we theoretically show that the water transport from the cathode to the anode depends primarily on the design of the cathode gas diffusion layer (GDL). We investigate experimentally the effects of the design parameters of the cathode GDL, including the PTFE (polytetrafluoroethylene) content in the backing layer (BL), and the carbon loading and the PTFE content in the microporous layer (MPL) on the water transport and the performance of the passive DMFC with the help of a reference electrode. The results indicate that on one hand, these parameters can be adjusted to decrease the water concentration loss of the anode performance, but on the other hand, they can also cause an increase in the oxygen concentration loss of the cathode performance. Hence, an optimal balance in minimizing the both concentration losses is the key to maximize the cell performance.     

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.     

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.     

Effect of operating conditions on the performance of a direct methanol fuel cell with PtRuMo/CNTs as anode catalyst

PtRu/CNTs and PtRuMo/CNTs catalysts have been synthesized by microwave-assisted polyol process and used as the anode catalysts for a direct methanol fuel cell (DMFC). The catalysts were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectrometry (XPS). The effect of different anode catalysts, membrane electrode assembly (MEA) activation, methanol concentration, methanol flow rate, oxygen flow rate and cell temperature on the DMFC performance has been investigated. The results show that the PtRu or PtRuMo particles with face-centered cubic structure are uniformly distributed on CNTs, and the addition of Mo to PtRu/CNTs makes the binding energies of each Pt species shift to lower values. PtRuMo/CNTs is a promising anode catalyst for DMFCs, and the appropriate operating conditions of the DMFC with PtRuMo/CNTs as the anode catalyst are MEA activation for 10 h, 2.0–2.5 M methanol at the flow rate of 1.0–2.0 mL/min, and oxygen at the flow rate of 100–150 mL/min. The DMFC performance increases significantly with an increase in cell temperature.     

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.