Effect of cathode gas diffusion layer on water transport and cell performance in direct methanol fuel cells

The optimal design of the cathode gas diffusion layer (GDL) for direct methanol fuel cells (DMFCs) is not only to attain better cell performance, but also to achieve better water management for the DMFC system. In this work, the effects of both the PTFE loading in the cathode backing layer (BL) as well as in the micro-porous layer (MPL) and the carbon loading in the MPL on both water transport and cell performance were investigated experimentally. The experimental data showed that with the presence of a hydrophobic MPL in the GDL, the water-crossover flux through the membrane decreased slightly with increasing the PTFE loading in the BL. However, a higher PTFE loading in the BL not only lowered cell performance, but also resulted in an unstable discharging process. It was also found that the PTFE loading in the MPL had little effect on the water-crossover flux, but its effect on cell performance was substantial: the 40-wt% PTFE loading in the MPL was found to be the optimal value to achieve the best performance. The experimental results further showed that increasing the carbon loading in the MPL significantly lowered the water-crossover flux, but a too high carbon loading would decrease the cell performance as the result of the increased oxygen transport resistance; the 2.0-mg C cm⁻² carbon loading was found to exhibit the best performance.     

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.     

Noble metal nanowires incorporated Nafion membranes for reduction of methanol crossover in direct methanol fuel cells

We electrodeposited noble metal (palladium, platinum) nanowires into the hydrophilic pores of Nafion membrane for mitigating the problem of methanol crossover in direct methanol fuel cells (DMFCs). The DMFC performance result shows that the composite membranes yield lower rate of methanol crossover and better cell performance than the pure Nafion^® membrane. At low current densities, the Pd nanowire incorporated Nafion membrane shows the best performance. In comparison, the highest performance is achieved at higher current densities with the Pt nanowire modified Nafion membrane. Based on the above findings, we suggest that for the Pd nanowire incorporated Nafion membrane, the mechanism for the suppression of the methanol crossover is mainly the blocking effect due to the ‘narrowed’ hydrophilic channels in Nafion membrane. For the Pt nanowire modified Nafion membrane, the mechanism includes both increasing the membrane tortuosity and so-called ‘on-way consumption’ of methanol on the Pt nanowires deposited into the Nafion membrane when the fuel cell is discharging.     

Double microporous layer cathode for membrane electrode assembly of passive direct methanol fuel cells

A novel membrane electrode assembly (MEA) is described that utilizes a double microporous layer (MPL) structure in the cathode of a passive direct methanol fuel cell (DMFC). The double MPL cathode uses Ketjen Black carbon as an inner-MPL and Vulcan XC-72R carbon as an outer-MPL. Experimental results indicate that this double MPL structure at the cathode provides not only a higher oxygen transfer rate, but enables more effective back diffusion of water; thus, leading to an improved power density and stability of the passive DMFC. The maximum power density of an MEA with a double MPL cathode was observed to be ca. 33.0 mW cm⁻², which is found to be a substantial improvement over that for a passive DMFC with a conventional MEA. A. C. impedance analysis suggests that the increased performance of a DMFC with the double MPL cathode might be attributable to a decreased charge transfer resistance for the cathode oxygen reduction reaction.     

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.     

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.     

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.     

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.     

Enhancement of water retention in the membrane electrode assembly for direct methanol fuel cells operating with neat methanol

It is desirable to operate a direct methanol fuel cell (DMFC) with neat methanol to maximize the specific energy of the DMFC system, and hence increasing its runtime. A way to achieve the neat-methanol operation is to passively transport the water produced at the cathode through the membrane to the anode to facilitate the methanol oxidation reaction (MOR). To achieve a performance of the MOR similar to that under the conventional diluted methanol operation, both the water transport rate and the local water concentration in the anode catalyst layer (CL) are required to be sufficiently high. In this work, a thin layer consisting of nanosized SiO₂ particles and Nafion ionomer (referred to as a water retention layer hereafter) is coated onto each side of the membrane. Taking advantage of the hygroscopic nature of SiO₂, the cathode water retention layer can help maintain the water produced from the cathode at a higher concentration level to enhance the water transport to the anode, while the anode retention layer can retain the water that is transported from the cathode. As a result, a higher water transport rate and a higher water concentration at the anode CL can be achieved. The formed membrane electrode assembly (MEA) with the added water retention layers is tested in a passive DMFC and the results show that this MEA design yields a much higher power density than the MEA without water retention layers does.     

In situ analysis on water transport in a direct methanol fuel cell durability test

In present work, a 600 h durability test and in situ measurements of water transport were carried out on a single direct methanol fuel cell (DMFC) at atmospheric pressure and 80 °C. Effect of water transport on the single cell performance was investigated in detail, which indicated that the accumulated water in the hydrophobic micropores of the cathode gas diffusion layer (GDL) aggravated the cathode flooding, and consequently led to a temporary and reversible degradation of the cell performance. Further investigation revealed that cathode flooding could be alleviated by blowing the cathode with dry air for 150 h at open circuit condition and the partially recovered cell performance within the durability could be obtained in consequence. Water analysis combined with the scanning electron microscopy (SEM), contact angle measurement and energy dispersive X-ray (EDX) was used to explore the characteristics of cathode GDL before and after the durability test. Results showed that the variation of the microstructure and hydrophobic properties for both sides of the cathode GDL is probably one of the inherent reasons for the irreversible degradation of the cell performance besides the electro-catalysts deterioration.     

A review on methanol crossover in direct methanol fuel cells: challenges and achievements

Direct methanol fuel cells have the potential to power future microelectronic and portable electronic devices because of their high energy density. One of the major obstacles that currently prevent the widespread applications of direct methanol fuel cells is the methanol crossover through the polymer‐electrolyte membrane. Methanol crossover is closely related to several factors including membrane structure and morphology, membrane thickness, and fuel cell operating conditions such as temperature, pressure, and methanol feed concentration. This work presents a comprehensive overview of the state‐of‐the‐art technology for the most important factors, affecting methanol crossover in direct methanol fuel cells. In addition, the current and future directions of the research and development activities, aiming to reduce the methanol crossover are reviewed and discussed in order to improve the performance of direct methanol fuel cells. Copyright © 2011 John Wiley & Sons, Ltd.     

Numerical study of the effect of the GDL structure on water crossover in a direct methanol fuel cell

A two-dimensional two-phase non-isothermal mass transport model is developed to numerically investigate the behavior of water transport through the membrane electrode assembly (MEA) of a direct methanol fuel cell. The model enables the visualization of the distribution of the liquid saturation through the MEA and the analysis of the distinct effects of the three water transport mechanisms: diffusion, convection and electro-osmotic drag, on the water-crossover flux through the membrane. A parametric study is then performed to examine the effects of the structure design of the gas diffusion layer (GDL) on water crossover. The results indicate that the flow-channel rib coverage on the GDL surface and the deformation of the GDL can cause an uneven distribution of the water-crossover flux along the in-plane direction, especially at higher current densities. It is also found that both the contact angle and the permeability of the cathode GDL can significantly influence the water-crossover flux. The water-crossover flux can be reduced by improving the hydrophobicity of the cathode GDL.     

Molecular sieve as an effective barrier for methanol crossover in direct methanol fuel cells

Methanol crossover is still a significant barrier to the commercialization of direct methanol fuel cells with wide-used Nafion® membrane. Herein, molecular sieve is introduced into the design of polymer electrolyte membrane to alleviate methanol crossover. The UZM-9 zeolite with an intermediate window size of 0.42 nm can effectively separate hydrated methanol (ca. 1.10 nm) and hydrated proton (ca. 0.23 nm). The methanol diffusion rate through the membrane is effectively suppressed after modified with UZM-9, which is about four times lower than the origin Nafion® membrane. The resulted peak power density reached 80 mW cm⁻² with 2 mol L⁻¹ methanol solution feed, which is 2.5-fold higher than that of direct methanol fuel cell with commercial Nafion® membrane. These results open a promising route to alleviate methanol crossover in direct methanol fuel cells.     

Effect of water concentration in the anode catalyst layer on the performance of direct methanol fuel cells operating with neat methanol

This paper reports on a chromatography-based method for determining the water concentration in the anode catalyst layer (CL) of a direct methanol fuel cell (DMFC). By this method, the effect of the water concentration in the anode CL on the product distribution of the methanol oxidation reaction (MOR), the anode potential, and the cell internal resistance is experimentally investigated in a DMFC operating with neat methanol. Interestingly, it is found that the main product of the anode MOR is still carbon dioxide even when the water concentration in the anode CL is extremely low. The experimental data also show that an increase in the water concentration in the anode CL decreases the internal resistance, the production of by-products (methyl formate and methylal), and the anode potential. As the mole ratio of water to methanol increases beyond a critical value, however, both the internal resistance and the anode potential tend to be stabilized at the points under diluted methanol operating conditions.     

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.     

Effect of variation of hydrophobicity of anode diffusion media along the through-plane direction in direct methanol fuel cells

Reducing methanol crossover from the anode to cathode in direct methanol fuel cells (DMFCs) is critical for attaining high cell performance and fuel utilization, particularly when highly concentrated methanol fuel is fed into DMFCs. In this study, we present a novel design of anode diffusion media (DM) wherein spatial variation of hydrophobicity along the through-plane direction is realized by special polytetrafluoroethylene (PTFE) coating procedure. According to the capillary transport theory for porous media, the anode DM design can significantly affect both methanol and water transport processes in DMFCs. To examine its influence, three different membrane-electrode assemblies are fabricated and tested for various methanol feed concentrations. Polarization curves show that cell performance at high methanol feed concentration conditions is greatly improved with the anode DM design with increasing hydrophobicity toward the anode catalyst layer. In addition, we investigate the influence of the wettability of the anode microporous layer (MPL) on cell performance and show that for DMFC operation at high methanol feed concentration, the hydrophilic anode MPL fabricated with an ionomer binder is more beneficial than conventional hydrophobic MPLs fabricated with PTFE. This paper highlights that controlling wetting characteristics of the anode DM and MPL is of paramount importance for mitigating methanol crossover in DMFCs.     

Current density measurements in direct methanol fuel cells

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

Effects of anode microporous layers made of carbon powder and nanotubes on water transport in direct methanol fuel cells

The effects of the design parameters of the anode diffusion layer (DL), including the PTFE loading in the backing layer (BL), and the carbon and PTFE loading in the microporous layer (MPL), on water transport through the membrane and the performance of a liquid-feed direct methanol fuel cell (DMFC) are experimentally investigated. The results indicate that increasing the PTFE loading in the BL and introducing a MPL could decrease water crossover through the membrane without sacrificing cell performance when the feed methanol concentration is increased. It is also found that changing the PTFE loading in the MPL has little effect on water crossover, whereas increasing the carbon loading in the MPL could noticeably decrease the water-crossover flux. Nevertheless, the ability of the MPL to reduce water crossover is limited by the presence of a number of mud cracks. To reduce further the water-crossover flux, a crack-free MPL made of multi-walled carbon nanotubes (MWCNTs) and PTFE is proposed. Tests indicate that the DMFC with the nanotube MPL results in a much lower water-crossover flux than a conventional carbon-powder MPL. More importantly, the use of the nanotube MPL allows the DMFC to be operated with a higher methanol concentration, and thereby increases the fuel cell system energy density.     

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.     

Water management in direct methanol fuel cells

Water management is an important challenge in portable direct methanol fuel cells. Reducing the water and methanol loss from the anode to the cathode enables the use of highly concentrated methanol solutions to achieve enhanced performances. In this work, the results of a simulation study using a previous developed model for DMFCs are presented. Particular attention is devoted to the water distribution across the cell. The influence of different parameters (such as the cathode relative humidity (RH), the methanol concentration and the membrane, catalyst layer and diffusion media thicknesses) over the water transport and on the cell performance is studied. The analytical solutions of the net water transport coefficient, for different values of the cathode relative humidity are successfully compared with recent published experimental data putting in evidence that humidified cathodes contribute to a decrease on the water crossover. As a result of the modelling results, a tailored MEA build-up with the common available commercial materials is proposed to achieve low methanol and water crossover and high power density, operating at relatively high methanol concentrations. A thick anode catalyst layer to promote methanol oxidation, a thin anode gas diffusion layer as methanol carrier to the catalyst layer and a thin polymer membrane to lower the water crossover coefficient between the anode and cathode are suggested.