The influences of multi-walled carbon nanotube addition to the anode on the performance of direct methanol fuel cells

Different amounts of multi-walled carbon nanotubes (MWCNTs) are added to anode catalyst layer in the membrane electrode assemblies (MEAs) of direct methanol fuel cells (DMFCs). The MEA with 0.5 wt.% carbon nanotubes (CNTs) shows the best performance in DMFC. In the protonic conductivity tests, a 0.5 wt.% amount of MWCNTs results in the highest protonic conductivity. SEM and TEM observations show that a continuous and uniform distribution of Nafion ionomer layer is formed on the MWCNT surface. Therefore, the dispersed MWCNTs in the catalyst layer are considered to be helpful for developing the pathways of protons transport.     

Water management in a passive direct methanol fuel cell

Passive direct methanol fuel cells (DMFCs) are under development for use in portable applications because of their enhanced energy density in comparison with other fuel cell types. The most significant obstacles for DMFC development are methanol and water crossover because methanol diffuses through the membrane generating heat but no power. The presence of a large amount of water floods the cathode and reduces cell performance. The present study was carried out to understand the performance of passive DMFCs, focused on the water crossover through the membrane from the anode to the cathode side. The water crossover behaviour in passive DMFCs was studied analytically with the results of a developed model for passive DMFCs. The model was validated with an in‐house designed passive DMFC. The effect of methanol concentration, membrane thickness, gas diffusion layer material and thickness and catalyst loading on fuel cell performance and water crossover is presented. Water crossover was lowered with reduction on methanol concentration, reduction of membrane thickness and increase on anode diffusion layer thickness and anode and cathode catalyst layer thickness. It was found that these conditions also reduced methanol crossover rate. A membrane electrode assembly was proposed to achieve low methanol and water crossover and high power density, operating at high methanol concentrations. The results presented provide very useful and actual information for future passive DMFC systems using high concentration or pure methanol. Copyright © 2012 John Wiley & Sons, Ltd.     

A three-dimensional mathematical model for liquid-fed direct methanol fuel cells

A three-dimensional, single-phase, multi-component mathematical model has been developed for a liquid-fed direct methanol fuel cell (DMFC). The traditional continuity, momentum, and species conservation equations are coupled with electrochemical kinetics in both the anode and cathode catalyst layer. At the anode side, the liquid phase is considered, and at the cathode side only the gas phase is considered. Methanol crossover due to both diffusion and electro-osmotic drag from the anode to the cathode is taken into consideration and the effect is incorporated into the model using a mixed-potential at the cathode. A finite-volume-based CFD technique is used to develop the in-house numerical code and the code is successfully used to simulate the fuel cell performance as well as the multi-component behavior in a DMFC. The modeling results of polarization curves compare well with our experimental data. Subsequently, the model is used to study the effects of methanol crossover, the effects of porosities of the diffusion layer and the catalyst layer, the effects of methanol flow rates, and the effects of the channel shoulder widths.     

A three-dimensional two-phase flow model for a liquid-fed direct methanol fuel cell

A three-dimensional, two-phase, multi-component model has been developed for a liquid-fed DMFC. The modeling domain consists of the membrane, two catalyst layers, two diffusion layers, and two channels. Both liquid and gas phases are considered in the entire anode, including the channel, the diffusion layer and the catalyst layer; while at the cathode, two phases are considered in the gas diffusion layer and the catalyst layer but only single gas phase is considered in the channels. For electrochemical kinetics, the Tafel equation incorporating the effects of two phases is used at both the cathode and anode sides. At the anode side the presence of gas phase reduces the active catalyst areas, while at the cathode side the presence of liquid water reduces the active catalyst areas. The mixed potential effects due to methanol crossover are also included in the model. The results from the two-phase flow mode fit the experimental results better than those from the single-phase model. The modeling results show that the single-phase models over-predict methanol crossover. The modeling results also show that the porosity of the anode diffusion layer plays an important role in the DMFC performance. With low diffusion layer porosity, the produced carbon dioxide cannot be removed effectively from the catalyst layer, thus reducing the active catalyst area as well as blocking methanol from reaching the reaction zone. A similar effect exits in the cathode for the liquid water.     

Effect of design of multilayer electrodes in direct methanol fuel cells (DMFCs)

In a direct methanol fuel cell (DMFC), optimized multilayer electrode design is critical to mitigate methanol crossover and improve cell performance. In this paper, we present a one-dimensional (1-D) two-phase model based on the saturation jump theory in order to explore the methanol and water transport characteristics using various multilayer electrode configurations. To experimentally validate the 1-D model, two different membrane electrode assemblies (MEAs) with and without an anode microporous layer (MPL) are fabricated and tested under various cell current density and methanol feed concentration conditions. Then, 1-D DMFC simulations are performed and the results compared to the experimental data. In general, the numerical predictions are in good agreement with the experimental data; thus, the 1-D DMFC simulations successfully model the effects of the anode MPL that were observed experimentally. In addition to the comparison study, additional numerical simulations are carried out to precisely examine the role of the anode and cathode MPLs and the effect of the hydrophobicity of the anode catalyst layer on the water and liquid saturation distributions inside the DMFCs. This paper demonstrates the quantitative accuracy of the saturation jump model for simulating multilayer DMFC MEAs and also provides greater insight into the operational characteristics of DMFCs incorporating multilayer electrodes.     

Experimental validation of a methanol crossover model in DMFC applications

A design of experiments (DOEs) coupled with a mathematical model was used to quantify the factors affecting methanol crossover in a direct methanol fuel cell (DMFC). The design of experiments examined the effects of temperature, cathode stoichiometry, anode methanol flow rate, clamping force, anode catalyst loading, cathode catalyst loading (CCL), and membrane thickness as a function of current and it also considered the interaction between any two of these factors. The analysis showed that significant factors affecting methanol crossover were temperature, anode catalyst layer thickness, and methanol concentration. The analysis also showed how these variables influence the total methanol crossover in different ways due to the effects on diffusion of methanol through the membrane, electroosmotic drag, and reaction rate of methanol at the anode and cathode. For example, as expected analysis showed that diffusion was significantly affected by the anode and cathode interfacial concentration, by the thickness of the anode catalyst layer and membrane, and by the diffusion coefficient in the membrane. Less obvious was the decrease in methanol crossover at low cathode flow rates were due to the formation of a methanol film at the membrane/cathode catalyst layer interface. The relative proportions of diffusion and electroosmotic drag in the membrane changed significantly with the cell current of the cell.     

A single-phase model for liquid-feed DMFCs with non-Tafel kinetics

An isothermal single-phase 3D/1D model for liquid-feed direct methanol fuel cells (DMFC) is presented. Three-dimensional (3D) mass, momentum and species transport in the anode channels and gas diffusion layer is modeled using a commercial, finite-volume based, computational fluid dynamics (CFD) software complemented with user supplied subroutines. The 3D model is locally coupled to a one-dimensional (1D) model accounting for the electrochemical reactions in both the anode and the cathode, which provides a physically sound boundary condition for the velocity and methanol concentration fields at the anode gas diffusion layer/catalyst interface. The 1D model – comprising the membrane–electrode assembly, cathode gas diffusion layer, and cathode channel – assumes non-Tafel kinetics to describe the complex kinetics of the multi-step methanol oxidation reaction at the anode, and accounts for the mixed potential associated with methanol crossover, induced both by diffusion and electro-osmotic drag. Polarization curves computed for various methanol feed concentrations, temperatures, and methanol feed velocities show good agreement with recent experimental results. The spatial distribution of methanol in the anode channels, together with the distributions of current density, methanol crossover and fuel utilization at the anode catalyst layer, are also presented for different opperating conditions.     

Construction of gradient catalyst layer anode by incorporating covalent organic framework to improve performance of direct methanol fuel cells

Improving cell performance is the most demanded task in direct methanol fuel cell (DMFC) research, although this fuel cell has several intrinsic features like high energy density, moderate operating temperature and environmentally friendly operation. The catalyst layer (CL) is the site of electrochemical reactions directly affecting the cell performance. Accordingly, the structure and preparation of the CL are crucial in optimizing performance. In this study, a novel gradient catalyst layer (G-CL) for the anode of DMFC is developed and better performance is obtained compared with that of single catalyst layer (S-CL) anode. A G-CL anode is composed of an outer CL of covalent organic framework (COF) materials-mixed catalyst near the microporous layer (MPL) and a conventional inner CL near the membrane side. Different loading of Pt catalyst in the two layers. Therefore, in the G-CL structure, there existed a catalyst concentration gradient and porosity gradient. Anode electrodes are characterized morphologically and electrochemically and the performance of individual cells containing such G-CL designs is measured. The results indicate that incorporation of the appropriate amount of COF materials enables the outer CL not only to have a larger electrochemical surface area (ECSA) and expose more catalytic active sites but also holds a strong proton transfer ability to improve the methanol oxidation reaction (MOR) performance. Due to the presence of the inner layer of the CL formed the methanol gradient oxidation process. With the same platinum-ruthenium (Pt–Ru) catalyst loading, the 5 wt.% COF G-CL anode structure exhibited lower methanol crossover and higher power density (nearly 11% increment) compared with that of the S-CL anode with high methanol concentration (8 M) at 60 °C, showing the promising potential in further applications.     

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.     

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.     

Real time measurements of methanol crossover in a DMFC

Methanol crossover is a serious problem in a direct methanol fuel cell (DMFC), which causes significant voltage loss and waste of fuel. Due to methanol crossover, most DMFCs must operate on a fuel with a very low methanol concentration; yet very low methanol concentration also causes a poor cell performance. Thus, it is very important to find the optimal operating conditions of methanol concentration and other operating parameters. In this research, methanol crossover rate in a DMFC is determined by measuring the carbon dioxide concentration at the cathode exit in real time. By measuring methanol crossover and cell performances at different inlet methanol concentrations and various operating conditions three types of characteristics are identified in the relationships between methanol crossover and cell current density. Further analysis of these relationships between methanol crossover and cell performances reveals the optimal methanol concentration and other operating parameters, at which the cell reaches optimal performance without incurring excessive methanol crossover. Furthermore, transient peaks of methanol crossover have been identified when the cell voltage suddenly changes. Analyses of these peaks show that they are caused by the hysteresis of methanol concentration at the interface between the anode catalyst layer and the membrane.     

DMFC anode polarization: Experimental analysis and model validation

Anode two-phase flow has an important influence on DMFC performance and methanol crossover. In order to elucidate two-phase flow influence on anode performance, in this work, anode polarization is investigated combining experimental and modelling approach. A systematic experimental analysis of operating conditions influence on anode polarization is presented. Hysteresis due to operating condition is observed; experimental results suggest that it arises from methanol accumulation and has to be considered in evaluating DMFC performances and measurements reproducibility. A model of DMFC anode polarization is presented and utilised as tool to investigate anode two-phase flow. The proposed analysis permits one to produce a confident interpretation of the main involved phenomena. In particular, it confirms that methanol electro-oxidation kinetics is weakly dependent on methanol concentration and that methanol transport in gas phase produces an important contribution in anode feeding. Moreover, it emphasises the possibility to optimise anode flow rate in order to improve DMFC performance and reduce methanol crossover.     

Comparison of numerical simulation results with experimental current density and methanol-crossover data for direct methanol fuel cells

The simulation results of a one-dimensional (1D) direct methanol fuel cell (DMFC) model are compared with the current density and methanol-crossover data that are experimentally measured under several different cell designs and operating conditions. No fitting parameters are employed for the comparison and model input parameters obtained from the literature are consistently used for all the cases of comparison. The numerical predictions agree well with the experimental data and the 1D DMFC model successfully captures key experimental trends that are observed in the cell current density and methanol-crossover data. This clearly illustrates that the present DMFC model can be applicable for optimizing DMFC component designs and operating conditions. In addition, the model simulations further indicate that the reduction of the methanol concentration in the anode catalyst layer is critical to simultaneously suppress both the electro-osmotic drag (EOD) and the diffusion aspects of methanol crossover.     

Direct ethanol fuel cell anode simulation model

The electrochemical behavior of a direct ethanol feed proton exchange membrane fuel cell (DEFC) operating under steady-state isothermal conditions at 1 atm at both anode and cathode sides is considered. A mathematical model that describes in one phase and one dimension the ethanol mass transport throughout the anode compartment and proton exchange membrane is developed. The influence of the operation parameters such as current density, temperature, catalyst layer thickness and ethanol feed concentration on both anode overpotential and ethanol crossover rate has been examined. According to the simulation results, it was found that the anode overpotential is more sensitive to the protonic conductivity than to the diffusion coefficient of ethanol in the catalyst layer. It was concluded that in the case of low current density values and high concentrations of ethanol aqueous solutions, ethanol crossover is a serious problem for a DEFC performance. Finally, it was found a good agreement between simulation and experimental results.     

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.     

A DMFC stack operating with hydrocarbon blend membranes and Pt–Ru–Sn–Ce/C and Pd–Co/C electrocatalysts

Direct methanol fuel cell (DMFC) stacks consisting of 5 cells and 20 cells were assembled with low-cost hydrocarbon blend membranes and new electrocatalysts with better methanol tolerance and stability. The hydrocarbon blend membranes consisting of an acidic polymer (sulfonated poly (ether ether ketone), SPEEK) and a basic polymer (polysulfone-2-amide-benzimidazole, PSf-ABIm) exhibited low methanol crossover, high conductivity, and good mechanical stability. The Pt–Ru–Sn–Ce/C anode catalyst exhibited better stability than the commercial PtRu/C catalyst, while the cathode catalyst Pd–Co/C showed better methanol tolerance than the commercial Pt/C catalyst. A maximum power of around 20 W was achieved with a DMFC stack consisting of 20 membrane-electrode assemblies (MEAs) fabricated with the above membranes and electrocatalysts. The results demonstrate the feasibility of utilizing these acid-base blend membranes and novel catalysts for DMFC applications.     

An effective layout of polyaniline nanofibers incorporated in membrane-electrode assembly as methanol transport regulator for direct methanol fuel cells

This study reports a novel strategy by using polyaniline nanofibers (PANFs) to modify membrane-electrode assembly (MEA) for improving direct methanol fuel cell (DMFC) performance. First of all, a series of PANFs emeraldine salt was synthesized and characterized. Then, we investigated the effect of PANFs layout in MEA on DMFC performance. Three different placements to incorporate the as-synthesized PANFs in anodes include (1) placing a layer of PANFs between catalyst layer (CL) and proton exchange membrane (PEM), (2) mixing with catalyst slurry and coating onto gas diffusion layer (GDL), and (3) placing a layer of PANFs between CL and GDL. Polarization curves indicate that the third method is superior to the others and is adopted as the incorporation layout thereafter. Both methanol transport resistance and methanol crossover of the PANFs-modified MEA are studied further. The DMFC incorporated with H₂SO₄-doped PANFs obtained after the re-doping process with 2 mol L⁻¹ H₂SO₄ performs a power density as high as 53 mW cm⁻², about 20% higher than that of the pristine one without PANFs incorporation. However, an excessive doping level may result in a higher methanol transport resistance due to PANFs aggregation and thus deteriorate DMFC performance. This study provides a simple and effective way by placing a layer of PANFs between CL and GDL in anode to act as methanol transport regulator and improve DMFC performance consequently.     

Modeling and optimizing the performance of a passive direct methanol fuel cell

Passive direct methanol fuel cells (DMFCs) are promising energy sources for portable electronic devices. Different from DMFCs with active fuel feeding systems, passive DMFCs with nearly stagnant fuel and air tend to bear comparatively less power densities. In the aspect of cell performance optimization, there could be significant differences in cell design parameters between active and passive DMFCs. A numerical model that could simulate methanol permeation and the pertinent mixed potential effect in a DMFC was used to help seek for possibilities of optimizing the cell performance of a passive DMFC by studying impacts from variations of cell design. The subjects studied include catalysis of the anode and the cathode, membrane thickness, membrane conductivity, and methanol concentration. In contrast to general understandings on a DMFC with active fuel and reactant gas, our simulation results for a passive DMFC used in this study indicated that the catalysis of the cathode appeared to be the most important parameter. The maximum power density was predicted to improve by 38% with the thickness of the cathodic catalyst layer doubled and by 36% with the catalyst loading doubled. The improvement on cell performance would multiply if we simultaneously adopted the most optimal parameters during the simulation study.     

Design of a MEA with multi-layer electrodes for high concentration methanol DMFCs

According to the conventional MEA test, methanol and water crossover are the main factors to determine performance of a passive DMFC. Thus, to ensure the high cell performance of a passive DMFC using high concentration methanol of 50–95 vol%, the MEA in this study introduces the barrier layer to limit the crossover of high concentration methanol, a hydrophobic layer to reduce water crossover, and a hydrophilic layer to enhance the water recovery from the cathode to the anode. The functional layers of the MEA have the effect of improving the performance of the passive DMFC by decreasing the methanol and water crossover. In spite of the operation with 95 vol% methanol, the MEA with multi-layer electrodes for high concentration methanol DMFCs shows a maximum power density of 35.1 mW cm⁻² and maintains a high power density of 30 mW cm⁻² (0.405 V) under constant current operation.     

An algebraic semi-empirical model for evaluating fuel crossover fluxes of a DMFC under various operating conditions

In a fuel cell of low temperature, especially a direct methanol fuel cell (DMFC), fuel crossover phenomenon plays a significant role not only in its performance evaluation and analysis, but also in the optimum control under various operating conditions. A quantitative prediction of the fuel crossover flux thus becomes essential. Generally speaking, the theoretical approaches to the issue will be dramatically complex and less practical. On the other hand, experimental schemes are time-consuming and less capable of further analysis and applications. Consequently, a semi-empirical model that incorporates dominant physical parameters and operating variables is proposed in this paper to adequately evaluate the phenomenon of fuel crossover fluxes. It is stated analytically in the form of an algebraic function, in which the fuel concentration, the current density, and the temperature of the fuel cell are considered. It is therefore more suitable for a variety of in-situ applications. In the proposed model, the methanol concentration gradient in the anode backing layer, the anode catalyst layer, and the membrane are analyzed. The transfer behavior of methanol is modeled on the basis of diffusion and electro-osmosis mechanisms. By means of the proposed model, one can obtain a better prediction and a clearer picture of the effects of operating variables and physical parameters on methanol crossover fluxes.