Numerical investigations of effect of membrane electrode assembly structure on water crossover in a liquid-feed direct methanol fuel cell

A two-phase mass-transport model is employed to investigate the water transport behaviour through the membrane electrode assembly (MEA) of a liquid-feed direct methanol fuel cell (DMFC). Emphasis is placed on examining the effects of each constituent component design of the MEA, including catalyst layers, microporous layers and membranes, on each of the three water crossover mechanisms: electro-osmotic drag, diffusion, and convection. The results show that lowering the diffusion flux of water or enhancing the convection flux of water (termed as the back-flow flux) through the membrane are both feasible to suppress water crossover in DMFCs. It is found that the reduction in the diffusion flux of water can be mainly achieved through optimum design of the anode porous layers, as the effect of the cathode porous region on water crossover by diffusion is relatively smaller. On the other hand, the design of the cathode porous layers plays a more important role in increasing the back-flow flux of water from the cathode to anode.     

A theoretical model of the membrane electrode assembly of liquid feed direct methanol fuel cell with consideration of water and methanol crossover

An algebraic model of the membrane electrode assembly of the direct methanol fuel cell is developed, which considers the simultaneous liquid water and methanol crossover effects, and the associated electrochemical reactions. The respective anodic and cathodic polarization curves can be predicted using this model. Methanol concentration profile and flux are correlated explicitly with the operating conditions and water transport rate. The cathode mixed potential effect induced by the methanol crossover is included and the subsequent cell voltage loss is identified. Water crossover is influenced by the capillary pressure equilibrium and hydrophobic property within the cathode gas diffusion layer. The model can be used to evaluate the cell performance at various working parameters such as membrane thickness, methanol feed concentration, and hydrophobicity of the cathode gas diffuser.     

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.     

An approach for determining the liquid water distribution in a liquid-feed direct methanol fuel cell

In determining the liquid water distribution in the anode (or the cathode) diffusion medium of a liquid-feed direct methanol fuel cell (DMFC) with a conventional two-phase mass transport model, a current-independent liquid saturation boundary condition at the interface between the anode flow channel and diffusion layer (DL) (or at the interface between the cathode flow channel and cathode DL) needs to be assumed. The numerical results resulting from such a boundary condition cannot realistically reveal the liquid distribution in the porous region, as the liquid saturation at the interface between the flow channel and DL varies with current density. In this work, we propose a simple theoretical approach that is combined with the in situ measured water-crossover flux in the DMFC to determine the liquid saturation in the anode catalyst layer (CL) and in the cathode CL. The determined liquid saturation in the anode CL (or in the cathode CL) can then be used as a known boundary condition to determine the water distribution in the anode DL (or in the cathode DL) with a two-phase mass transport model. The numerical results show that the water distribution becomes much more realistic than those predicted with the assumed boundary condition at the interface between the flow channel and DL.     

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.     

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

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

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.     

Mass balance research for high electrochemical performance direct methanol fuel cells with reduced methanol crossover at various operating conditions

Mass balance research in direct methanol fuel cells (DMFCs) provides a more practical method in characterizing the mass transport phenomena in a membrane electrode assembly (MEA). This method can be used to measure methanol utilization efficiency, water transport coefficient (WTC), and methanol to electricity conversion rate of a MEA in DMFCs. First, the vital design parameters of a MEA are recognized for achieving high methanol utilization efficiency with increased power density. In particular, the structural adjustment of anode diffusion layer by adding microporous layer (MPL) is a very effective way to decrease WTC with reduced methanol crossover due to the mass transfer limitation in the anode. On the other hand, the cathode MPL in the MEA design can contribute in decreasing methanol crossover. The change of structure of cathode diffusion layer is also found to be a very effective way in improving power density. In contrast, the WTC of DMFC MEAs remains virtually constant in the range of 3.4 and 3.6 irrespective of the change of the cathode GDL. The influence of operating condition on the methanol utilization efficiency, WTC, and methanol to electricity conversion rate is also presented and it is found that these mass balance properties are strongly affected by temperature, current density, methanol concentration, and the stoichiometry of fuel and air.     

Improved mass transfer using a pore former in cathode catalyst layer in the direct methanol fuel cell

The cathode catalyst layer in direct methanol fuel cells (DMFCs) was prepared using polystyrene beads as a pore former. Field emission scanning electron microscopy showed that the catalyst layer with the pore former contained pores with a uniform shape and size. Mercury intrusion porosimetry showed that the pore former increased the volume of secondary pores in the catalyst layer. The electrochemical properties of the membrane electrode assembly (MEA) were evaluated by current–voltage polarization measurements, electrochemical impedance spectroscopy and cyclic voltammetry. These results suggest that the catalyst layer with the pore former reduces the mass transfer resistance and improves the cell performance by approximately 50% through modification of its morphology.     

Long-term durability test for direct methanol fuel cell made of hydrocarbon membrane

A long-term durability test has been conducted for a direct methanol fuel cell (DMFC) using the commercial hydrocarbon membrane and Nafion ionomer bonded electrodes for 500 h. Membrane electrode assembly (MEA) made by a decal method has experienced a performance degradation about 34% after 500 h operation. Cross-sectional analysis of the MEA shows that the poor interfacial contact between the catalyst layers and membrane in the MEA has further deteriorated after the durability test. Therefore, the internal resistance of a cell measured by electrochemical impedance spectroscopy (EIS) has considerably increased. The delamination at the interfaces is mainly attributed to incompatibility between polymeric materials used in the MEA. Furthermore, X-ray diffraction (XRD) analysis reveals that the catalyst particles have grown; thereby decreasing the electrochemical surface area. Electron probe micro analysis (EPMA) shows a small amount of Ru crossover from anode to cathode; and its effect on the performance degradation has been analyzed.     

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.     

Modelling and experimental studies on a direct methanol fuel cell working under low methanol crossover and high methanol concentrations

A number of issues need to be resolved before DMFC can be commercially viable such as the methanol crossover and water crossover which must be minimised in portable DMFCs.     

In situ measurements of water crossover through the membrane for direct methanol fuel cells

We show analytically that the water-crossover flux through the membrane used for direct methanol fuel cells (DMFCs) can be in situ determined by measuring the water flow rate at the exit of the cathode flow field. This measurement method enables investigating the effects of various design and geometric parameters as well as operating conditions, such as properties of cathode gas diffusion layer (GDL), membrane thickness, cell current density, cell temperature, methanol solution concentration, oxygen flow rate, etc., on water crossover through the membrane in situ in a DMFC. Water crossover through the membrane is generally due to electro-osmotic drag, diffusion and back convection. The experimental data showed that diffusion dominated the total water-crossover flux at low current densities due to the high water concentration difference across the membrane. With the increase in current density, the water flux by diffusion decreased, but the flux by back convection increased. The corresponding net water-transport coefficient was also found to decrease with current density. The experimental results also showed that the use of a hydrophobic cathode GDL with a hydrophobic MPL could substantially reduce water crossover through the membrane, and thereby significantly increasing the limiting current as the result of the improved oxygen transport. It was found that the cell operating temperature, oxygen flow rate and membrane thickness all had significant influences on water crossover, but the influence of methanol concentration was negligibly small.     

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.     

On the electrochemical impedance spectroscopy of direct methanol fuel cell

The direct methanol fuel cell (DMFC) was operated under a variety of current densities to monitor the electrochemical impedance spectroscopy (EIS) for understanding its reaction mechanism. Based on the EIS analysis, the impedance of the cell reaction is divided into three components, two of them are current dependent and the remainder is current independent. Through detailed exploration of the impedance components, the high-frequency impedance was attributed to interfacial behavior, the medium-frequency impedance to electrochemical reactions, and the low-frequency impedance to the adsorption/relaxation of CO. Based on EIS analysis, a qualitative model is proposed to delineate the reaction mechanisms of DMFC, which is confirmed quantitatively by one set of equivalent circuit elements. The experimental data are satisfactorily consistent with the results simulated from the proposed model.     

Nafion/polyaniline/silica composite membranes for direct methanol fuel cell application

This work investigates the characterization and performance of polyaniline and silica modified Nafion membranes. The aniline monomers are synthesized in situ to form a polyaniline film, whilst silica is embedded into the Nafion matrix by the polycondensation of tetraethylorthosilicate. The physicochemical properties are studied by means of X-ray diffraction and Fourier transform infrared techniques and show that the polyaniline layer is formed on the Nafion surface and improves the structural properties of Nafion in methanol solution. Nafion loses its crystallinity once exposed to water and ethanol, whilst the polyaniline modification allows crystallinity to be maintained under similar conditions. By contrast, the proton conductivities of polyaniline modified membranes are 3–5-fold lower than that of Nafion. On a positive note, methanol crossover is reduced by over two orders of magnitude, as verified by crossover limiting current analysis. The polyaniline modification allows the membrane to become less hydrophilic, which explains the lower proton conductivity. No major advantages are observed by embedding silica into the Nafion matrix. The performance of a membrane electrode assembly (MEA) using commercial catalysts and polyaniline modified membranes in a cell gives a peak power of 8 mW cm⁻² at 20 °C with 2 M methanol and air feeding. This performance correlates to half that of MEAs using Nafion, though the membrane modification leads to a robust material that may allow operation at high methanol concentration.     

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.     

Enhanced performance of a passive direct methanol fuel cell with decreased Nafion aggregate size within the anode catalytic layer

The decrease in Nafion ionomer size within the anode catalytic layer for a passive direct methanol fuel cell (DMFC) results in a significant enhancement in fuel cell’s performance. Dynamic light scattering measurement demonstrates that the agglomerate size of Nafion ionomer in the solution decreases and the aggregate particle size distribution becomes narrow until a monodispersed Nafion ionomer was obtained with an increase in heat treatment temperature. The improved performance of the passive DMFC with smaller Nafion ionomer agglomerates within the anode catalytic layer can be ascribed to a decrease in charge-transfer resistance of anodic reaction obtained by electrochemical impedance analysis and to an improvement in catalyst utilization verified by cyclic voltammetric measurement. Furthermore, the small congeries formed between catalyst nanoparticles and Nafion ionomers could lead to a decrease in Nafion loading within the catalytic layer. This study confirms that the decrease in Nafion aggregation within the catalytic ink is beneficial to an improvement in both catalyst and Nafion ionomer utilization, thus enhancing fuel cell’s performance.     

A semi-empirical model for efficiency evaluation of a direct methanol fuel cell

Energy density and power density are two of the most significant performance indices of a fuel cell system. Both the indices are closely related to the operating conditions. Energy density, which can be derived from fuel cell efficiency, is especially important to small and portable applications. Generally speaking, power density can be easily obtained by acquiring the voltage and current density of an operating fuel cell. However, for a direct methanol fuel cell (DMFC), it is much more difficult to evaluate its efficiency due to fuel crossover and the complex architecture of fuel circulation. The present paper proposes a semi-empirical model for the efficiency evaluation of a DMFC under various operating conditions. The power density and the efficiency of a DMFC are depicted by explicit functions of operating temperature, fuel concentration and current density. It provides a good prediction and a clear insight into the relationship between the aforementioned performance indices and operating variables. Therefore, information including power density, efficiency, as well as remaining run-time about the status of an operating DMFC can be in situ evaluated and predicted. The resulting model can also serve as an important basis for developing real-time control strategies of a DMFC system.     

Effects of MEA preparation on the performance of a direct methanol fuel cell

The effects of membrane electrode assemblies (MEAs) fabrication methods (spraying and scraping methods) and the hot-pressing pretreatment of anode electrodes on the performance of direct methanol fuel cells (DMFCs) were investigated. The MEA prepared with scraped anode catalyst layer without the hot-pressing pretreatment showed the highest power density of 67 mW cm⁻² at 80 °C and ambient pressure. The scraping method proved to be a little more profitable for improving the cell performance than the spraying method. Atomic force microscopy (AFM) analysis revealed relatively smooth surface of the scraped anode catalyst layer compared with that of sprayed anode catalyst layer. Scanning electron microscopy (SEM) images showed that a suitable number of cracks which were uniformly distributed on the surface of scraped catalyst layer formed a porous structure. It was demonstrated that the surface structure and roughness of the anode catalyst layer had less effect on the performance of the anode electrode in a DMFC. The hot-pressing pretreatment of the anode electrode decreased the performance of the MEA due to the difficulty for electrons and mass transport in the anode electrode, namely the increase of internal cell resistance.