Comprehensive one-dimensional,semi-analytical,mathematical model for liquid-feed polymer electrolyte membrane direct methanol fuel cells

Polymer electrolyte membrane direct methanol fuel cells (PEM-DMFCs) have several advantages over hydrogen-fuelled PEM fuel cells; but sluggish methanol electrochemical oxidation and methanol crossover from the anode to the cathode through the PEM are two major problems with these cells. In the present work, a comprehensive one-dimensional, single phase, isothermal mathematical model is developed for a liquid-feed PEM-DMFC, taking into account all the necessary mass transport and electrochemical phenomena. Diffusion and convective effects are considered for methanol transport on the anode side and in the PEM, whereas only diffusional transport of species is considered on the cathode side. A multi-step reaction mechanism is used to describe the electrochemical oxidation of methanol at the anode. Stefan–Maxwell equations are used to describe multi-component diffusion on the cathode side and Tafel type of kinetics is used to describe the simultaneous methanol oxidation and oxygen reduction reactions at the cathode. The model fully accounts for the mixed potential effect caused by methanol crossover at the cathode. It shows excellent agreement with literature data of the limiting current density for different low methanol feed concentrations at different operating temperatures. At high methanol feed concentrations, oxygen depletion on the cathode side, due to excessive methanol crossover, results in mass-transport limitations. The model can be used to optimize the geometric and physical parameters with a view to extracting the highest current density while still keeping a tolerably low methanol crossover.     

Behavior of a methanol fuel cell in transitory regime

The operation of a polymeric electrolyte methanol/air fuel cell connected to a storage tank with anolyte batch recycle is analyzed. When the cell is discharged at constant current, far below the anode reaction limiting current density, the concentration in the tank is found to decrease with time following a lineal variation. At zero time, a high CO₂ concentration is detected in the air leaving the cathode compartment, which increased when higher methanol concentration is used in the anode compartment. This effect is associated to the crossover of methanol through the membrane. The amount of CO₂ in the air outlet is important, and both this quantity and the crossover flux decrease when methanol concentration diminish in the anolyte. A model derived from electrochemical reactor analysis, that correlates methanol concentration changes in the storage tank, and methanol concentration at the anodic compartment exit with the amount consumed in the cell reaction and the flow through the membrane is developed.     

A hydrodynamic network model for interdigitated flow fields

The flow field is one of the main components of a fuel cell, which distributes the reactants to the active area of the cell and evacuates the products formed. Interdigitated flow field (IFF) is one among the different types of flow field designs that forces the reactants or products to flow through the electrode, thereby increasing the cell performance by decreasing concentration polarization loss, however, at the cost of higher-pressure drop. Prior understanding of the reactant and water vapour distribution in a flow field helps in obtaining the best flow field design. In the present paper, a model for the flow distribution and the pressure drop in an IFF has been developed using the analogy between fluid flow and electrical network in which the pressure is made analogous to the voltage and the flow rate to the current. The model, which ultimately reduces to the solution of a set of simultaneous algebraic equations, is capable of predicting the flow split among a set of inlet and outlet channels of an interdigitated flow field as well as the overall pressure drop for laminar, turbulent and two-phase flow conditions for arbitrary number of parallel channels. The results from the hydrodynamic network model have been validated against CFD simulations. This model can therefore be used for the optimization of interdigitated flow field design.     

Methanol and water crossover in a passive liquid-feed direct methanol fuel cell

Methanol crossover, water crossover, and fuel efficiency for a passive liquid-feed direct methanol fuel cell (DMFC) were all experimentally determined based on the mass balance of the cell discharged under different current loads. The effects of different operating conditions such as current density and methanol concentration, as well as the addition of a hydrophobic water management layer, on the methanol and water crossover were investigated. Different from the active DMFC, the cell temperature of the passive DMFC increased with the current density, and the changes of methanol and water crossover with current density were inherently coupled with the temperature rise. When feeding with 2–4 M methanol solution, with an increase in current density, both the methanol crossover and the water crossover increased, while the fuel efficiency first increased but then decreased slightly. The results also showed that a reduction of water crossover from the anode to the cathode was always accompanied with a reduction of methanol crossover. Not only did the water management layer result in lower water crossover or achieve neutral or reverse water transport, but it also lowered the methanol crossover and increased the fuel efficiency.     

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.     

An analytical model for hydrogen and nitrogen crossover rates in proton exchange membrane fuel cells

In this paper, the hydrogen and nitrogen crossover through the membrane in proton exchange membrane fuel cells, are investigated by developing a semi-empirical analytical model. Different factors that affect the gas crossover rates were considered including pressure drop in gas diffusion layer (GDL) and catalyst layer (CL), operating temperature, relative humidity (RH) of the reactants, GDL compression, and the current density effect on the membrane temperature. The model is validated by published experimental data. It is found that RH is the most important parameter, followed by temperature. The hydrogen pressure drop through GDL and CL greatly depends on the GDL substrate properties, microporous layer (MPL) and CL. When permeability is low, an increase in current density reduces gas crossover. GDL compression, when MPL is used, was found to have a low impact on gas crossover. Gas crossover is improved with current density due to an increase in membrane temperature.     

Methanol fuel processor and PEM fuel cell modeling for mobile application

The use of hydrocarbon fed fuel cell systems including a fuel processor can be an entry market for this emerging technology avoiding the problem of hydrogen infrastructure. This article presents a 1 kW low temperature PEM fuel cell system with fuel processor, the system is fueled by a mixture of methanol and water that is converted into hydrogen rich gas using a steam reformer. A complete system model including a fluidic fuel processor model containing evaporation, steam reformer, hydrogen filter, combustion, as well as a multi-domain fuel cell model is introduced. Experiments are performed with an IDATECH FCS1200™ fuel cell system. The results of modeling and experimentation show good results, namely with regard to fuel cell current and voltage as well as hydrogen production and pressure. The system is auto sufficient and shows an efficiency of 25.12%. The presented work is a step towards a complete system model, needed to develop a well adapted system control assuring optimized system efficiency.     

Performance of dimethoxymethane and trimethoxymethane in liquid-feed direct oxidation fuel cells

The present study involves the evaluation of dimethoxymethane (DMM) (formaldehyde dimethyl acetal, or methylal) and trimethoxymethane (TMM) (trimethyl orthoformate) in direct oxidation liquid-feed fuel cells as novel oxygenated fuels. We have demonstrated that sustained oxidation of TMM at high current densities can be achieved in half-cells and liquid-feed polymer electrolyte fuel cells 1, 2 and 3. In the present study, the performance of dimethoxymethane and trimethoxymethane was compared with that of methanol in 2″ × 2″ (25 cm² electrode area) and 4″ × 6″ (160 cm² electrode area) direct oxidation fuel cells. The impact of various parameters upon cell performance, such as cell temperature, anode fuel concentration, cathode fuel pressure and flow (O₂ and air), was investigated. Fuel crossover rates in operating fuel cells were also measured for methanol, DMM, and TMM and characterized in terms of concentration and temperature effects. Although DMM and more particularly TMM may present some logistical advantages over that of methanol, such as possessing a higher boiling point, higher flash point, and lower toxicity, the overall performance was observed to be inferior to that of methanol under typical fuel cell operating conditions.     

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.     

Performance prediction of proton exchange membrane fuel cells using a three-dimensional model

In this study a steady-state three-dimensional computational fluid dynamics (CFD) model of a proton exchange membrane fuel cell is developed and presented for a single cell. A complete set of conservation equations of mass, momentum, species, energy transport, and charge is considered with proper account of electrochemical kinetics based on Butler–Volmer equation. The catalyst layer structure is considered to be agglomerate. This model enables us to investigate the flow field, current distribution, and cell voltage over the fuel cell which includes the anode and cathode collector plates, gas channels, catalyst layers, gas diffusion layers, and the membrane. The numerical solution is based on a finite-volume method in a single solution domain. In this investigation a CFD code was used as the core solver for the transport equations, while mathematical models for the main physical and electrochemical phenomena were devised into the solver using user-developed subroutines. Three-dimensional results of the flow structure, species concentrations and current distribution are presented for bipolar plates with square cross section of straight flow channels. A polarization curve is obtained for the fuel cell under consideration. A comparison between the polarization curves obtained from the current study and the corresponding available experimental data is presented and a reasonable agreement is obtained. Such CFD model can be used as a tool in the development and optimization of PEM fuel cells.     

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.     

Three-port single-phase three-wire power converter interface for micro grid

This paper proposes a three-port single-phase three-wire (TPSPTW) power converter interface integrating an isolated current-fed full-bridge power converter (ICFPC), a three-port power converter (TPPC), a fuel cell and a battery set for micro grid (MG).The ICFPC is used to control the output power of fuel cell and to step-up its output voltage to the voltage of high-voltage DC port of the TPPC. The TPPC can manage the power conversion between the fuel cell, the battery set, the loads and the utility. This power converter interface charges the battery set, outputs AC power and acts as an active power filter (APF) in the grid-connection mode, supplies uninterruptible power to the loads when it operates in the stand-alone mode. The fuel cell outputs a programmed power regardless of whether the power converter interface operates in the grid-connection mode or in the stand-alone mode. The programmed power outputted from the fuel cell is the average power of load under the stand-alone mode. The battery set is used to respond to the varied power of loads under the stand-alone mode. A prototype is developed to verify the performance of power converter interface, and the experimental results are as expected.     

A mathematical model for simulating methanol permeation and the mixed potential effect in a direct methanol fuel cell

A mathematical model for simulating methanol permeation and the pertinent mixed potential effect in a direct methanol fuel cell (DMFC) is presented. In this model a DMFC is divided into seven compartments namely the anodic flow channel, the anodic diffusion layer, the anodic catalyst layer, the proton exchange membrane (PEM), the cathodic catalyst layer, the cathodic diffusion layer and the cathodic flow channel. All compartments are considered to have finite thickness, and within every one of them a set of governing equations are given to stipulate methanol transport and oxygen transport. For the flow channels, fluid dynamics, which could substantially lower the local methanol concentration within catalyst layers is taken into account. With the knowledge of local concentrations of the species, the electrochemical reaction rates within both catalyst layers can be quantified by a kinetic Tafel expression. For the anodic catalyst layer the local external current generated by methanol oxidation is computed; for the cathodic catalyst layer, in addition to the local external current generated by oxygen reduction, the local internal current as a result of methanol permeation is also computed. With the information of the local internal current, the mixed potential effect, which is responsible for adversely lowering the cell voltage can be analyzed.     

A novel composite membranes based on sulfonated montmorillonite modified Nafion for DMFCs

A novel functional organoclay was prepared using POP-backboned quaternary ammonium salts that contained sulfonic acid (–SO₃H) to improve the performance of Nafion^® membranes used in direct methanol fuel cells. Modified layered silicate clays were cast with Nafion^®. The performance of the Nafion^®/MMT-POPD400-PS composite membranes was evaluated in terms of methanol permeability, proton conductivity and cell performance. The methanol permeability of the composite membrane declined as the MMT-POPD400-PS content increased. The MMT was functionalized using organic sulfonic acid to enhance proton conductivity. The proton conductivity of the composite membrane exceeded that of pristine Nafion^®. These effects essentially improved the single-cell performance of DMFC.     

Evaluation of silver-coated stainless steel bipolar plates for fuel cell applications

In this study, computer-aided design and manufacturing (CAD/CAM) technology were applied to develop and produce stainless steel bipolar plates for DMFC (direct methanol fuel cell). Effect of surface modification on the cell performance of DMFC was investigated. Surface modifications of the stainless steel bipolar plates were made by the electroless plating method. A DMFC consisting of silver coated stainless steel as anode and uncoated stainless steel as cathode was assembled and evaluated. The methanol crossover rate (R_c) of the proton exchange membrane (PEM) was decreased by about 52.8%, the efficiency (E_f) of DMFC increased about 7.1% and amounts of methanol electro-oxidation at the cathode side (M_co) were decreased by about 28.6%, as compared to uncoated anode polar plates. These measurements were determined by the transient current and mathematical analysis.     

DMFC performance and methanol cross-over: Experimental analysis and model validation

A combined experimental and modelling approach is proposed to analyze methanol cross-over and its effect on DMFC performance. The experimental analysis is performed in order to allow an accurate investigation of methanol cross-over influence on DMFC performance, hence measurements were characterized in terms of uncertainty and reproducibility. The findings suggest that methanol cross-over is mainly determined by diffusion transport and affects cell performance partly via methanol electro-oxidation at the cathode. The modelling analysis is carried out to further investigate methanol cross-over phenomenon. A simple model evaluates the effectiveness of two proposed interpretations regarding methanol cross-over and its effects. The model is validated using the experimental data gathered. Both the experimental analysis and the proposed and validated model allow a substantial step forward in the understanding of the main phenomena associated with methanol cross-over. The findings confirm the possibility to reduce methanol cross-over by optimizing anode feeding.     

A CFD model with semi-empirical electrochemical relationships to study the influence of geometric and operating parameters on DMFC performance

A three-dimensional computational fluid dynamics (CFD) model is developed to investigate the influence of geometric and operating parameters on performance of a direct methanol fuel cell (DMFC). Semi-empirical relationships are introduced to describe the electrochemical behaviors required in the CFD governing equations. Coefficients in these semi-empirical relationships are fitted using experimental data. Two geometric configurations with serpentine channels at the anode and cathode are considered in this work. Temperature, methanol concentration, and methanol flow rate are selected as the operating parameters. Due to the computational effort of CFD, an adaptive metamodeling method is developed to reduce the number of data-fitting iterations for obtaining the coefficients in the semi-empirical relationships. The effectiveness of the method is demonstrated by fitting the model using the experimental data collected from the first geometric configuration of the DMFC and comparing the predicted performance of the second configuration with its experimental performance. A commercial CFD system, Fluent 12.0, was used in this research.     

Low methanol crossover and high performance of DMFCs achieved with a pore-filling polymer electrolyte membrane

We compared the performance of the membrane electrode assembly for direct methanol fuel cells (DMFCs) composed of a pore-filling polymer electrolyte membrane (PF membrane) with that composed of a commercial Nafion-117 membrane. In DMFC tests, the methanol crossover flux was 23% lower in the PF membrane than in the Nafion-117 membrane even though the thickness of the PF membrane was 43% that of Nafion-117. This led to a higher DMFC performance and the lower overpotential of the cathode of the PF membrane. Feeding an aqueous 10 M methanol solution at 50 °C produced a low cathode overpotential, as low as 0.40 V at 0.2 A in the PF membrane, whereas the potential was 0.65 V at 0.2 A in the Nafion-117 membrane. In contrast, the ohmic loss and anode overpotential were almost the same in the two membranes. We confirmed that a reduction in methanol crossover using the PF membrane results in lower cathode overpotential and higher DMFC performance. In addition, the electro-osmotic coefficient was estimated as 1.3 in the PF membrane and 2.6 in Nafion-117, based on a water mass-balance model and values showing that the PF membrane prevents the flooding of the cathode at a low gas flow rate using. A highly concentrated methanol solution can be applied as a fuel without decreasing DMFC performance using PF membranes.     

Carbon dioxide vent for direct methanol fuel cells

Passive, stand-alone, direct methanol fuel cells require a pressure management system that releases CO₂ produced in the anode chamber. However, this must be done without allowing the methanol fuel to escape. In this paper, two siloxane membranes are investigated and shown to selectively vent CO₂ from the anode chamber. The addition of hydrophobic additives, 1,6-divinylperfluorohexane and 1,9-decadiene, improved the selectivity of the siloxane membranes. The best performing CO₂ vent was obtained with 50:50 wt% poly(1-trimethyl silyl propyne) and 1,6-divinylperfluorohexane.     

Simplified model for the direct methanol fuel cell anode

A kinetic model for the anode of the direct methanol fuel cell (DMFC) is presented. The model is based on the generally accepted dual site mechanism of methanol oxidation, in aqueous solution, on well characterized Pt–Ru catalyst and it can predict the performance of the electrode as a function of cell temperature, anode potential and methanol concentration. In addition the model also generates data regarding the surface coverage of significant adsorbates involved in methanol oxidation on the dual site catalyst.