Role of hydrophobic anode MPL in controlling water crossover in DMFC

The importance of reducing water crossover from anode to cathode in a direct methanol fuel cell (DMFC) has been well documented, especially if highly concentrated methanol fuel is to be used. A low-α membrane electrode assembly (MEA) with thin membrane is key to achieving this goal. The low water crossover from anode to cathode for these types of MEAs has traditionally been attributed to the use of a hydrophobic cathode micro-porous layer (MPL). However, it has recently been discovered that a hydrophobic anode MPL also reduces the water crossover, possibly even more significantly than a hydrophobic cathode MPL. In this work, we develop and use a 1D, two-phase transport model that accounts for capillary-induced liquid flow in porous media to explain how a hydrophobic anode MPL controls the water crossover from anode to cathode. We further show that a lower water crossover can lead to a lower methanol crossover via dilution of methanol in the anode catalyst layer. Finally, we perform a parametric study and show that a thicker anode MPL with greater hydrophobicity and lower permeability is more effective in reducing the water crossover.     

Water and methanol crossover in direct methanol fuel cells—Effect of anode diffusion media

Various anode diffusion media have been experimentally studied to reduce water crossover in a direct methanol fuel cell (DMFC). A two-phase water transport model was also employed to theoretically study their effects on water transport and saturation level in a DMFC anode. It is found that wettability of the anode microporous layer (MPL) has a dramatic effect on water crossover or the water transport coefficient (α) through the membrane. Under different current densities, the MEA with a hydrophobic anode MPL has consistently low α, several times smaller than those with a hydrophilic MPL or without an anode MPL. Methanol transport in the anode is found to be not influenced by a hydrophobic anode MPL but inhibited by a hydrophilic one. Constant-current discharge shows that the MEA with hydrophobic anode MPL displays much smaller voltage fluctuation than that with the hydrophilic one. A modeling study of anode water transport reveals that the liquid saturation in the anode is lowered significantly with the increase of anode MPL contact angle, which is thus identified as a key parameter to minimize water crossover in a DMFC.     

Comparative studies of configurations and preparation methods for direct methanol fuel cell electrodes

Catalyst-coated membrane (CCM) and catalyzed diffusion medium (CDM) prepared either by brush painting method or by spraying method were compared for direct methanol fuel cell (DMFC) anode and cathode. The pore structure and the morphology of the electrodes were characterized by mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM). Internal resistance corrected polarization curves were employed to separate the contribution of each compartment of the membrane electrode assembly (MEA) to the overall polarization. It was shown that the increased mass transport resistance in the anode diffusion layer made the anode in CDM form act as the methanol barrier. The CCM configuration and the increased pores in micron scales in the catalyst layer were in favor of improving the performance of both anode and cathode. Accounting for the effect of methanol permeation, the combination of the anode in CDM form prepared by brush painting method and the cathode in CCM form prepared by spraying method was finally selected as the optimized configuration for MEA, which had the highest DMFC performance under near-ambient conditions.     

Alcohol Crossover Behavior in Direct Alcohol Fuel Cells (DAFCs) System

The alcohols (methanol, ethanol, and 1‐propanol) crossover behavior of through fuel cell membrane electrode assembly (MEA) in direct alcohol fuel cell (DAFC) system was studied. We divided five different factors which affect alcohol crossover behavior through MEA to analyze alcohol crossover behavior. Those are membrane effect, physical blocking effect of anode, alcohol oxidation effect of anode electrocatalysts, physical blocking effect of cathode, and alcohol oxidation effect of cathode. Among these five factors, the four factors caused by two different electrodes (anode and cathode) were evaluated by fabricating various types of MEA. In the case of alcohols through membrane without any electrode was increased when the cell temperature was raised from room temperature to 100 °C, but it was decreased above the cell temperature of 100 °C. Among the electrode effects on alcohol crossover rate, physical blocking effect of electrodes played dominant role below 100 °C. However alcohol oxidation effects of electrodes was predominant above the 100 °C.     

Development and characterization of a silicon-based micro direct methanol fuel cell

A silicon-based micro direct methanol fuel cell (μDMFC) for portable applications has been developed and its electrochemical characterization carried out in this study. Anode and cathode flowfields with channel and rib width of 750 μm and channel depth of 400 μm were fabricated on Si wafers using the microelectromechanical system (MEMS) technology. A membrane-electrode assembly (MEA) was specially fabricated to mitigate methanol crossover. This MEA features a modified anode backing structure in which a compact microporous layer is added to create an additional barrier to methanol transport thereby reducing the rate of methanol crossing over the polymer membrane. The cell with the active area of 1.625 cm² was assembled by sandwiching the MEA between two micro-fabricated Si wafers. Extensive cell polarization testing demonstrated a maximum power density of 50 mW/cm² using 2 M methanol feed at 60 °C. When the cell was operated at room temperature, the maximum power density was shown to be about 16 mW/cm² with both 2 and 4 M methanol feed. It was further found that the present μDMFC still produced reasonable performance under 8 M methanol solution at room temperature.     

A two-dimensional, two-phase mass transport model for liquid-feed DMFCs

A two-dimensional, isothermal two-phase mass transport model for a liquid-feed direct methanol fuel cell (DMFC) is presented in this paper. The two-phase mass transport in the anode and cathode porous regions is formulated based on the classical multiphase flow in porous media without invoking the assumption of constant gas pressure in the unsaturated porous medium flow theory. The two-phase flow behavior in the anode flow channel is modeled by utilizing the drift-flux model, while in the cathode flow channel the homogeneous mist-flow model is used. In addition, a micro-agglomerate model is developed for the cathode catalyst layer. The model also accounts for the effects of both methanol and water crossover through the membrane. The comprehensive model formed by integrating those in the different regions is solved numerically using a home-written computer code and validated against the experimental data in the literature. The model is then used to investigate the effects of various operating and structural parameters, such as methanol concentration, anode flow rate, porosities of both anode and cathode electrodes, the rate of methanol crossover, and the agglomerate size, on cell performance.     

Fluorination of Vulcan XC-72R for cathodic microporous layer of passive micro direct methanol fuel cell

The effect of adding fluorinated Vulcan XC-72R into the microporous layer (MPL) of the cathode in a passive micro direct methanol fuel cell (μDMFC) has been investigated. Upon fluorination with fluoro-alkyl silane (FAS), the surface of XC-72R becomes more hydrophobic, as indicated by contact angle measurements. The performance of the membrane electrode assembly (MEA) is improved significantly when fluorinated Vulcan XC-72R is used in MPL of the cathode. The maximum power density of a passive μDMFC reached ca. 36.2 mW cm⁻² at room temperature, and the constant-current discharging test exhibits enhanced stability. Also observed is a decreased water transport coefficient (α), calculated from discharging test, attributable to the greater hydrophobicity resulting in higher liquid pressure on the cathode, which forces more water to flow back to the anode. Additionally, A.C. impedance analysis indicates that the improvement in performance results from the decrease of charge transfer resistance of the cathodic reaction.     

Mathematical Model of Proton Exchange Membrane Fuel Cell with Consideration of Water Management

One‐dimensional model on the membrane electrode assembly (MEA) of proton exchange membrane fuel cell is proposed, where the membrane hydration/dehydration and the possible water flooding of the respective cathode and anode gas diffusion layers are considered. A novel approach of phase‐equilibrium approximation is proposed to trace the water front and the detailed saturation profile once water emerges in either anode or cathode gas diffusion layer. The approach is validated by a semi‐analytical method published earlier. The novel approach is applicable to the polarization regime from open circuit voltage to the limiting current density under practical operation conditions. Oxygen diffusion is limited by water accumulation in the cathode gas diffusion layer as current increases, caused by excessive water generation at the cathode catalyst layer and the electro‐osmotic drag across the membrane. The existence of liquid water in the anode gas diffusion layer is predicted at low current densities if high degrees of humidification in both anode and cathode feeds are employed. The influences of inlet relative humidity, imposed pressure drop, and cell temperature are correlated well with the cell performance. In addition, the overpotentials attributed from individual components of the MEA are delineated against the cell current densities.     

Pore‐forming technology and performance of MEA for direct methanol fuel cells

BACKGROUND: The commercialization of DMFCs is seriously restricted by its relatively low power density. Lots of work has been concentrated on catalysts with high activity, the optimization of flow path design, development of new kinds of proton exchange membrane and modification of Nafion membrane. Meanwhile, very few reports have involved the structure optimization of the membrane electrode assembly (MEA). To improve the performance of direct methanol fuel cells (DMFCs), the catalyst layer (CL) structures of anode and cathode were optimized by utilizing ammonium carbonate as pore forming agent. RESULTS: The polarization curves showed that in catalyst slurry the optimal content of ammonium carbonate was 50 wt%, and the DMFC performance was enhanced from 75.65 mW cm^?2 to 167.42 mW cm^?2 at 55 °C and 0.2 MPa O₂. Electrochemical impedance spectroscopy and electrochemical active surface area (EASA) testing revealed that the improved performance of optimized MEAs could be mainly attributed to the increasing EASA and the enhanced mass transfer rate of CLs. But poor methanol crossover limited the performance enhancement of MEAs with porous anodes. CONCLUSION: With regard to improving cell performance, this pore‐forming technology is better applied to the cathode catalyst layer to improve its structure rather than the anode catalyst layer. © 2012 Society of Chemical Industry     

自呼吸式直接甲醇燃料电池性能及其传质特性

针对有效面积为1 cm2的自呼吸式直接甲醇燃料电池（direct methanol fuel cell,DMFC）单电池,阳极采用燃料罐供液,将阴极侧集流体和夹具设计为一体式结构,并用自制的七合一膜电极组件对其进行测试,讨论了催化剂类型、扩散层材料、集流体结构等因素对其性能的影响,分析了电池内部的传质特性,优化了电池特别是其在中高电流密度条件下的性能。实验结果表明：采用Pt黑、Pt-Ru黑催化剂制作的自呼吸式DMFC能强化反应物的传质;采用碳布制作的膜电极更倾向于获得更高的极限电流密度;低电流密度时,因甲醇渗透电池电压随着甲醇浓度的增加而降低,但在中高电流密度下,电池性能随甲醇浓度的增大先升高后降低;平行集流体有利于阴阳极生成物的排出和反应物的传质,因此易获得较高的电池性能。     

Effect of wettability of anode microporous layer on performance and operation duration of passive air-breathing direct methanol fuel cells

The influence of the wettability of the anode microporous layer (MPL) on both cell performance and operation duration of air-breathing direct methanol fuel cells (DMFCs) was investigated. The experimental results demonstrated that a passive DMFC with a hydrophilic MPL (DMFC-L) in the anode gas diffusion layer (GDL) showed performance superior to that with a hydrophobic MPL (DMFC-B), when the performance evaluation was conducted by applying a holding time of 45 s at each current density. DMFC-B showed good performance at medium and high current densities when a holding time of 150 s was used. The observation of water accumulation on the cathode of DMFC-L indicated that the decreased performance resulted mainly from blockage of the oxygen supply path. The constant-current discharging test showed that DMFC-B exhibited a lower performance at the beginning of discharge. However, it showed a lower rate of water accumulation on the cathode and thereby relatively stable operation. Operating the passive DMFCs at high water evaporation rate confirmed the important role of the wettability of anode GDLs for cathode oxygen transport.     

直接甲醇液流燃料电池的二维两相模型

直接甲醇燃料电池(DMFC)的阴极水淹、甲醇渗透及贵金属催化剂的成本问题是DMFC商业化的主要障碍。直接甲醇液流燃料电池(DMRFC)使用Fe³⁺/Fe²⁺氧化还原电对取代DMFC阴极,克服了阴极的水淹、甲醇渗透和电池成本等问题。使用Comsol Multiphysics4.2a模拟软件,建立了一个DMRFC二维两相模型来预测电池性能,模拟结果显示增加阳极催化层厚度、减少阳极扩散层厚度和提高Fe³⁺浓度有利于提高电池的性能,但当阳极催化层厚度和甲醇浓度分别大于5×10^-5 m和1.41 mol/L时,电池性能并不能显著提高。     

Development of a Self‐Adaptive Direct Methanol Fuel Cell Fed with 20 M Methanol

A passive and self‐adaptive direct methanol fuel cell (DMFC) directly fed with 20 M of methanol is developed for a high energy density of the cell. By using a polypropylene based pervaporation film, methanol is supplied into the DMFC's anode in vapor form. The mass transport of methanol from the cartridge to the anodic catalyst layer can be controlled by varying the open ratio of the anodic bipolar plate and by tuning the hydrophobicity of anodic diffusion layer. An effective back diffusion of water from the cathode to the anode through Nafion film is carried out by using an additive microporous layer in the cathode that consists of 50 wt.% Teflon and KB‐600 carbon. Accordingly, the water back diffusion not only ensures the water requirement for the methanol oxidation reaction but also reduces water accumulation in the cathode and then avoids serious water flooding, thus improving the adaptability of the passive DMFC. Based on the optimized DMFC structure, a passive DMFC fed with 20 M methanol exhibits a peak power density of 42 mW cm^–2 at 25 °C, and no obvious performance degradation after over 90 h continuous operation at a constant current density of 40 mA cm^–2.     

Effect of anode backing layer on the cell performance of a direct methanol fuel cell

We investigated experimentally the effect of the anode backing layers consisting of carbon papers with different thicknesses and different polytetrafluoroethylene (PTFE) contents on the cell performance of a direct methanol fuel cell (DMFC). The membrane electrode assemblies were prepared using the decal method such that the effect of different anode backing layers could be studied with the same anode catalyst layer, the same membrane and the same cathode. We found that a too thin anode backing layer resulted in lower cell voltages in the entire current density region, whereas a too thick backing layer led to a lower limiting current density. The reduced cell performance as a result of thinning the backing layer may be attributed mainly to the increased under-rib mass transport polarization as a result of weaker under-rib convection in a thinner backing layer. The experimental results also showed that the use of a PTFE-treated backing layer resulted in a lower limiting current density, attributing primarily to the increased mass transfer resistance as a result of the PTFE treatment.     

Investigation of direct methanol fuel cell performance of sulfonated polyimide membrane

Sulfonated polyimide (SPI) membranes have been evaluated as electrolyte membranes in direct methanol fuel cells (DMFCs). The membrane-electrode assembly (MEA) was made by hot-pressing the membrane, an anode and a cathode, catalyzed with PtRu/CB (PtRu dispersed on carbon black) and Pt/CB bound with Nafion^® ionomer, respectively. The performance of the cell based on SPI was compared with that of Nafion^® 112 in various operation conditions such as cell temperature (T_cell), cathode relative humidity (RH), and methanol concentration (C_MeOH). The methanol crossover at the cell based on SPI was a half of Nafion^® 112, resulting in the improved cell efficiency. Advantage of the use of SPI became much distinctive from the conventional Nafion^® 112 when the DMFC was operated at a higher T_cell or a higher C_MeOH.     

Two-dimensional numerical modelling of a direct methanol fuel cell

The results of a numerical simulation of a direct methanol fuel cell (DMFC) with liquid methanol feed are presented. A two-dimensional numerical model of a DMFC is developed based on mass and current conservation equations. The velocity of the liquid is governed by gradients of membrane phase potential (electroosmotic effect) and pressure. The results show that, near the fuel channel, transport of methanol is determined mainly by the pressure gradient, whereas in the active layers, and in the membrane, diffusion transport dominates. Shaded zones, where there is a lack of methanol, are formed in front of the current collectors. The results reveal a strong influence of the hydraulic permeability of the backing layer K _p ^BL on methanol crossover through the membrane. If the value of K _p ^BL is comparable to that of the membrane and active layers, electroosmotic effects lead to the formation of an inverse pressure gradient. The flux of liquid driven by this pressure gradient is directed towards the anode and reduces methanol crossover.     

Experimental and numerical study on improvement performance by wave parallel flow field in a proton exchange membrane fuel cell

The performance and operation stability of proton exchange membrane fuel cells (PEMFCs) are closely related to the transportation of reactants and water management in the membrane electrode assembly (MEA) and flow field. In this paper, a new three-dimensional wave parallel flow field (WPFF) in cathode was designed and analyzed throughout simulation studies and an experimental method. The experimental results show that the performance of PEMFC with WPFF outperforms that of PEMFC with straight parallel flow field (SPFF). Specifically, the peak power density increased by 13.45% for the PEMFC with WPFF as opposed to PEMFC with SPFF. In addition, the flow field with area of 11.56 cm² was formed by the assembly of transparent end plate used for cathode and the traditional graphite plate used for anode. To understand the mechanism of the novel flow field improving the performance of PEMFC, a model of PEMFC was proposed based on the geometry, operating conditions and MEA parameters. The thickness of gas diffusion layers (GDL), catalytic layers (CL) and proton exchange membrane were measured by scanning electron microscope. The simulation result shows that compared with SPFF, the WPFF based PEMFC promote the oxygen transfer from flow channel to the surface of CL through GDL, and it was beneficial to remove the liquid water in the flow channel and the MEA.     

Effects of thickness and hydrophobicity of double microporous layer on the performance in proton exchange membrane fuel cells

In this paper, a multi-layer gas diffusion layer (GDL) is designed. The GDL consists of a single carbon paper backing layer and dual microporous layers (MPLs). Moreover, the effects of thickness and hydrophobicity of double MPL on the performance of proton exchange membrane fuel cells are investigated. From the test results of the water contact angle, conductivity, pore size distribution, and the polarization curve, it is found that the thickness adjustment increases the number of 0.5 to 7 μm and 20 to 100 μm pores in GDL, which is more conducive to water discharge. Therefore, the thickness adjustment is more favorable to the cell performance under high humidity. While the gradient hydrophobic design makes the MPL of the modified intermediate layer have a certain water-retaining capacity to humidify the reaction gas, which has better effect under low humidity. At last, the results show that the optimized GDL meets a limit power density of 1.772 W/cm² under 60% humidification and 1.600 W/cm² under 100% humidification.     

Ameliorating effect of silica addition in the anode-catalyst layer of the membrane electrode assemblies for polymer electrolyte fuel cells

Incorporation of silica particles through a sol-gel process into the anode-catalyst layer with a sol-gel modified Nafion-silica composite membrane renders easy retention of back-diffused water from the cathode to anode through the composite membrane electrolyte, increases the catalyst-layer wettability and improves the performance of the Polymer Electrolyte Fuel Cell (PEFC) while operating under relative humidity (RH) values ranging between 18% and 100% with gaseous hydrogen and oxygen reactants at atmospheric pressure. A peak power density of 300 mW cm⁻² is achieved at a load current-density value of 1200 mA cm⁻² for the PEFC employing a sol-gel modified Nafion-silica composite membrane and operating at 18% RH. Under similar operating conditions, the PEFC with a Membrane Electrode Assembly (MEA) comprising Nafion-silica composite membrane with silica in the anode-catalyst layer delivers a peak power density of 375 mW cm⁻². By comparison, the PEFC employing commercial Nafion membrane fails to deliver satisfactory performance at 18% RH due to the limited availability of water at its anode, acerbated electro-osmotic drag of water from anode to cathode and insufficient water back diffusion from cathode to anode causing the MEA to dehydrate.     

Investigation on cathode degradation of direct methanol fuel cell

The cathode degradation of a direct methanol fuel cell (DMFC) was investigated after a 240 h discontinuous galvostatic operation at 80 °C. The catalyst coated membrane (CCM) and the cathode diffusion layer were not combined so as to isolate electrochemical and mass transport processes. It was indicated by the EDS and SEM tests that the loss of the cathode electrochemical surface area (ESA) was associated with the decays of the Pt/C catalyst and the interfacial contact. Furthermore, Ru crossover and higher methanol crossover resulting from the anode failure aggravated the degradation of the cathode. On the other hand, the change of the pore structure led to a higher wettability of the cathode microporous layer. Therefore, the oxygen transport was suppressed due to the decrease of hydrophobic passages.