Local entropy generation and exergy analysis of the condenser in a direct methanol fuel cell system

This paper aims to identify the irreversibilities in the condenser of a direct methanol fuel cell (DMFC) system and present possible enhancements in its design through local entropy generation analysis (L-EGA). For this purpose, the local entropy generation terms originating from heat and mass calculated from results of a pseudo two-phase computational fluid dynamic (CFD) model of the condenser. Through this analysis, the total irreversibilities due to heat and mass transfer are calculated locally (e.g., film boundary layer, vapour-gas boundary layer) under the variable operating conditions of a DMFC (undersaturated, saturated, and supersaturated conditions of the cathode exhaust gas). Moreover, the exergy destruction ratio of condenser is found to estimate the exergy performance of the condenser. The results show that in the case of supersaturated cathode exhaust gas (CEG) flow, the entropy generation rate due to mass transfer in the film region is found as 0.032 W/(m·K) which is 18 times higher than that for the undersaturated CEG flow. However, entropy generation rate due to mass transfer decreases significantly when the hot flow is just over the film region. In the film region, the entropy generation rates originating from heat transfer are found as 0.0055 W/(m·K) (for the undersaturated case), 0.0032 W/(m·K) (for the saturated case), and 0.0015 W/(m·K) (for the supersaturated case). Moreover, the maximum exergy destruction ratio is found as 0.72 when the CEG is undersaturated and the CEG velocity is 0.18 m/s, while the lowest exergy destruction ratio is calculated as 0.28 when the CEG is saturated.     

Heat and mass transfer effects in a direct methanol fuel cell: A 1D model

Models are a fundamental tool for the design process of fuel cells and fuel cell systems. In this work, a steady-state, one-dimensional model accounting for coupled heat and mass transfer, along with the electrochemical reactions occurring in the DMFC, is presented. The model output is the temperature profile through the cell and the water balance and methanol crossover between the anode and the cathode. The model predicts the correct trends for the influence of current density and methanol feed concentration on both methanol and water crossover. The model estimates the net water transfer coefficient through the membrane, α, a very important parameter to describe water management in the DMFC. Suitable operating ranges can be set up for different MEA structures maintaining the crossover of methanol and water within acceptable levels. The model is rapidly implemented and is therefore suitable for inclusion in real-time system level DMFC calculations.     

Analysis of heat and mass transport in a miniature passive and semi passive liquid-feed direct methanol fuel cell

A two-dimensional, transient, multi-phase, multi-component, and non-isothermal model has been developed to solve the heat and mass transport in a passive and semi passive liquid-feed direct methanol fuel cell (DMFC). A semi passive DMFC uses channel at the cathode side to facilitate the oxidant transport. The transient characteristics of the temperature, methanol concentration, methanol crossover, useful current density and methanol evaporation are investigated. The results indicate that the temperature in the fuel cell increases during operation as much as 10 °C, due to the heat generation by internal phase change and the electrochemical reactions. However, it is revealed that the temperature distribution is nearly uniform at any time through all porous layers including the fuel cell and fuel delivery system. The effect of using an active feeding system in the cathode and passive methanol feeding in the anode (semi passive system) on the performance of a fuel cell is also studied. The active oxidant feeding to the cathode catalyst layer in the semi passive cell improved the fuel cell performance compared to that in a passive one. However, in general, the performance of passive cell is better than that in a semi passive one because of more temperature increase in the passive system.     

Two-dimensional two-phase thermal model for passive direct methanol fuel cells

A two-dimensional two-phase thermal model is presented for direct methanol fuel cells (DMFC), in which the fuel and oxidant are fed in a passive manner. The inherently coupled heat and mass transport, along with the electrochemical reactions occurring in the passive DMFC is modeled based on the unsaturated flow theory in porous media. The model is solved numerically using a home-written computer code to investigate the effects of various operating and geometric design parameters, including methanol concentration as well as the open ratio and channel and rib width of the current collectors, on cell performance. The numerical results show that the cell performance increases with increasing methanol concentration from 1.0 to 4.0 M, due primarily to the increased operating temperature resulting from the exothermic reaction between the permeated methanol and oxygen on the cathode and the increased mass transfer rate of methanol. It is also shown that the cell performance upgrades with increasing the open ratio and with decreasing the rib width as the result of the increased mass transfer rate on both the anode and cathode.     

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.     

Analyses of mass and heat transport interactions in a direct methanol fuel cell

In this paper, a two-dimensional, two-phase, non-isothermal model is presented to predict the electrochemical, mass transfer and heat transfer behaviors in a direct methanol fuel cell (DMFC). Governing equations including the momentum, continuity, heat transfer, proton and electron transport, species transport for water, methanol, and all the gas species (carbon dioxide, methanol vapor, water vapor, oxygen, and nitrogen) and the auxiliary equations are coupled to studying the various phenomena in DMFC. The modeling results agree well with the four different experimental data in an extensive range of operation conditions. A parametric study is also performed to examine the effects of the cell voltage on the different variables, such as cell temperature, liquid methanol concentration distribution, oxygen concentration distribution, and anode gas pressure distribution. The results show that the cell temperature is highly sensitive to the change in the cell voltage as well as methanol concentration distribution. Moreover, it is found that the cell voltage significantly influences the oxygen concentration distribution and the anode gas pressure distribution.     

Studies of the methanol crossover and cell performance behaviors of high temperature-direct methanol fuel cells (HT-DMFCs)

The high temperature-direct methanol fuel cell (HT-DMFC) based on phosphoric acid (PA)-doped polybenzimidazole (PBI) membranes shows promise as a passive-type DMFC system because it can operate using highly concentrated methanol fuel. In this paper, the methanol crossover and cell performance behaviors of the HT-DMFCs were investigated using a one-dimensional (1-D) HT-DMFC system model that fully accounts for the electrochemical reactions, key species transport and heat generation inside a cell, and the evaporation processes of liquid methanol/water fuel in the evaporator. The model was first validated against experimental HT-DMFC data measured over a wide range of methanol feed concentrations and operating current densities, and operating characteristics of HT-DMFCs were then explored in detail. Particular emphasis was placed on conducting a comparative study of HT-DMFCs with traditional liquid feed low temperature-DMFCs based on perfluorosulfonic acid membranes. The simulation results showed that a HT-DMFC can operate well under highly concentrated methanol fuel above 12 M due to the minimal degree of methanol crossover through the PA-doped PBI membrane.     

Non-isothermal modeling of direct methanol fuel cell

In this work, a two-dimensional, two-phase non-isothermal model is developed for DMFC. The natural convection heat transfer at the out surface of the current collector is considered as the thermal boundary conditions to obtain a more realistic simulation of the DMFC working conditions. The heat and mass transfer, along with the electrochemical reactions occurring in the DMFC are modeled and numerically solved by a self-developed simulation code. The numerical results show that cell performance is enhanced with the increase in the inlet temperature. The distribution of temperature in the DMFC mainly depends on the inlet temperature of the dilute methanol aqueous in the anode side. The mean temperature of MEA and temperature difference in MEA increase with the increase in current density and the profiles show the same trend. With the decrease in MEA thermal conductivity and the increase in the inlet temperature the temperature difference in MEA becomes larger.     

Influence and mitigation methods of reaction intermediates on cell performance in direct methanol fuel cell system

In direct methanol fuel cells (DMFCs), a dilute methanol and water mixture is generally used and recycled as a fuel to improve the performance and operation time with high fuel efficiency through reduced methanol crossover. Such recycling can, however, allow the continuous accumulation of some reaction intermediates in the circulating loop of dilute methanol during DMFC operation. Therefore, this study examines DMFC contamination sources and the electrochemical influence of recycled methanol fuel by physicochemical analysis of the organic and inorganic (metal) intermediates generated from the DMFC system components. Further, a novel method for mitigating the impact of the reaction intermediates on the performance of DMFC system is proposed.     

Multiple concentric spirals for the flow field of a proton exchange membrane fuel cell

The present analysis considers a three-dimensional non-isothermal model in a single phase of a PEM fuel cell with a flow field path in the shape of 1, 2, 3, 4, 6, and 8 concentric spirals. The current density contours, the water content and the entropy generated in all zones of the fuel cell are predicted. The analysis of the three-dimensional model includes the gas flow channels in the six geometric shapes mentioned above, the current collectors, gas diffusion layers, catalyst layers on both sides of the model, anode and cathode, and a proton exchange membrane in between. The energy equation, mass conservation, and transport of species equations are solved, including source terms that take into account the electrochemical effects occurring inside the cell. Also, the entropy generation equation is added to the governing equations of the model. The results allow a comparison to help to decide which of the 6 analyzed configurations improve the performance of the fuel cell, increasing the current density produced, reducing the pressure drop and producing the most uniform current density. The entropy generation analysis reveals the effects that cause the most significant losses (irreversibilities) in the cell. The Bejan number and the Π number are used to compare the irreversibilities produced by the matter flow and by the heat transfer for each one of the six models.     

Characterization of direct formic acid fuel cells by Impedance Studies: In comparison of direct methanol fuel cells

We characterized direct liquid fuel cells by electrochemical impedance spectroscopy (EIS) combined with reversible hydrogen electrode (RHE) under fuel cell operating conditions. EIS has been successfully implemented as an in-situ diagnostic tool using an impedance setup with RHE, capable of singling out individual contributions to the overall polarization of fuel cells and separating the anode and cathode contributions. While a direct methanol fuel cell (DMFC) anode was subject to substantial poisoning by reaction intermediates due to better accessibility of methanol to catalyst surface regardless of anode diffusion media, a direct formic acid fuel cell (DFAFC) anode suffered from significant mass transfer limitation depending on the anode diffusion media property and formic acid concentration. The high frequency resistance of a DFAFC cathode increased linearly with an increase of formic acid concentration by membrane dehydration effect. Interestingly, on both the DMFC and DFAFC cathodes, decrease in the mixed charge transfer resistance with an increase of fuel crossover was observed together with a drop in the cathode potential.     

Mass transport analysis of a passive vapor-feed direct methanol fuel cell

A two-dimensional, two-phase, non-isothermal model using the multi-fluid approach was developed for a passive vapor-feed direct methanol fuel cell (DMFC). The vapor generation through a membrane vaporizer and the vapor transport through a hydrophobic vapor transport layer were both considered in the model. The evaporation/condensation of methanol and water in the diffusion layers and catalyst layers was formulated considering non-equilibrium condition between phases. With this model, the mass transport in the passive vapor-feed DMFC, as well as the effects of various operating parameters and cell configurations on the mass transport and cell performance, were numerically investigated. The results showed that the passive vapor-feed DMFC supplied with concentrated methanol solutions or neat methanol can yield a similar performance with the liquid-feed DMFC fed with much diluted methanol solutions, while also showing a higher system energy density. It was also shown that the mass transport and cell performance of the passive vapor-feed DMFC depend highly on both the open area ratio of the vaporizer and the methanol concentration in the tank.     

Analysis of entropy generation in a hydrogen-enriched turbulent non-premixed flame

The analysis of local entropy generation and exergy loss was performed in a turbulent non-premixed H₂-enriched CH₄–air bluff-body flame. Detailed chemical kinetic, transport properties, and turbulence-chemistry interaction were taken into account in using laminar flamelet model for the simulation of combustion process via an in-house, finite volume code. The analysis was based on local entropy generation calculation. Results showed that thermal conduction made the most contribution to entropy generation followed by chemical reaction and mass diffusion, while the contribution of viscous dissipation was negligible. Entropy generation resulting from thermal conduction occurs in a large volume of the domain, while entropy generation resulting from chemical reaction and mass diffusion occurs only near the bluff surface. The effect of H₂ addition to fuel and air preheating on the entropy generation rate was investigated. It was observed that entropy generation and exergy loss were decreased by H₂ addition, mainly due to a decrease in the chemical reaction component of entropy generation, while entropy generation resulting from thermal conduction slightly increased and entropy generation resulting from mass diffusion remained almost constant. Entropy generation resulting from heat conduction by preheating combustion air decreased, while entropy generation resulting from chemical reaction and mass diffusion remained almost constant. The decrease of thermal conduction contribution in entropy generation is so significant that, by preheating air up to 750 K in the case of pure CH₄, chemical reaction becomes the main source of irreversibility. These investigations show that H₂ addition and preheating the combustion air both lead to the improvement of the second law efficiency, although the second law efficiency is more sensitive to flame structure and air temperature.     

A single-phase, non-isothermal model for PEM fuel cells

A proton exchange membrane (PEM) fuel cell produces a similar amount of waste heat to its electric power output, and tolerates a small temperature deviation from its design point for best performance and durability. These stringent thermal requirements present a significant heat transfer problem. In this work, a three-dimensional, non-isothermal model is developed to account rigorously for various heat generation mechanisms, including irreversible heat due to electrochemical reactions, entropic heat, and Joule heating arising from the electrolyte ionic resistance. The thermal model is further coupled with the electrochemical and mass transport models, thus permitting a comprehensive study of thermal and water management in PEM fuel cells. Numerical simulations reveal that the thermal effect on PEM fuel cells becomes more critical at higher current density and/or lower gas diffusion layer thermal conductivity. This three-dimensional model for single cells forms a theoretical foundation for thermal analysis of multi-cell stacks where thermal management and stack cooling is a significant engineering challenge.     

A Computational Study of Swirl Number Effects on Entropy Generation in Gas Turbine Combustors

In this paper, local and global entropy generation features are studied numerically in two research flames and a real combustor problem. The research flames are the well-known Burner Engineering Research Laboratory and Sandia flame D experimental flame databases and the real combustor is a gas-turbine can-type combustor. The main focus is on investigating the effect of the swirl number, in the range 0.0–2.4, on entropy generation characteristics due to different phenomena, including viscous, mass transfer, heat transfer, heat-mass coupling, reaction, and specifically radiation. For this purpose, the surface and volumetric local entropy generation rates are formulated based on the first-order spherical harmonics model known as “P1,” a frequently used model in combustion applications. It is observed that heat transfer and reactions are dominant causes of entropy generation with the leading contribution of reaction at lower swirl numbers and heat transfer at higher swirl values. The radiation entropy generation is slightly affected by the swirl number and is of prime importance only in near stoichiometric conditions. Moreover, it is indicated how this local entropy generation analysis can be used to discover the weaknesses in the design of a real combustor.     

A silicon‐based micro direct methanol fuel cell stack with a serial flow path design

A 6‐cell silicon‐based micro direct methanol fuel cell (μDMFC) stack utilized the serial flow path design was developed. The effect of the structure of flow path on the performance of the stack was investigated using polarization characterization and electrochemical impedance analysis. Further, the voltage distribution for individual cells under different current density was discussed. The results indicated that the μDMFC stack with the serial flow path design exhibited better performance than that utilized the parallel flow path due to uniform mass transfer of methanol as a result of the use of the serial flow path. Such a μDMFC stack generates a peak output power of ca. 187 mW, corresponding to an average power density of ca. 21.7 mWcm^‐2, and exhibits a steady‐state power output for more than 100 h. Copyright © 2011 John Wiley & Sons, Ltd.     

Mass and heat transport in direct methanol fuel cells

The direct methanol fuel cell (DMFC) is a better alternative to the conventional battery. The DMFC offers several advantages, namely, faster building of potential and longer-lasting fuel, however, there are still several issues that need to be addressed to design a better DMFC system. This article is a wide-ranging review of the most up-to-date studies on mass and heat transfer in the DMFC. The discussion will be focused on the critical problems limiting the performance of DMFCs. In addition, a technique for upgrading the DMFC with an integrated system will be presented, along with existing numerical models for modeling mass and heat transfer as well as cell performance.     

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.     

Entropy generation of viscous dissipative nanofluid flow in microchannels

An analytical study on the viscous dissipation effect on entropy generation in laminar fully developed forced convection of water–alumina nanofluid in circular microchannels is reported. In the first-law analysis, closed form solutions of the temperature distributions in the radial direction for the models with and without viscous dissipation term in the energy equation are obtained. The results show that the heat transfer coefficient decreases with nanoparticle volume fraction largely in the laminar regime of nanofluid flow in microchannel when the viscous dissipation effect is taken into account. In the second-law analysis, the two models are compared by analyzing their relative deviations in entropy generation for different Reynolds number and nanoparticle volume fraction. When the viscous dissipation is taken into account, the temperature distribution is prominently affected and consequently the entropy generation ascribable to the heat transfer irreversibility is significantly increased. The increase of entropy generation induced by the increase of nanoparticle volume fraction is attributed to the increase of both the thermal conductivity and viscosity of nanofluid which causes augmentation in the heat transfer and fluid friction irreversibilities, respectively. By incorporating the viscous dissipation effect, both thermal performance and exergetic effectiveness for forced convection of nanofluid in microchannels dwindle with nanoparticle volume fraction, contrary to the widespread conjecture that nanofluids possess advantage over pure fluid associated with higher overall effectiveness from the aspects of first-law and second-law of thermodynamics.     

Analysis of an active tubular liquid-feed direct methanol fuel cell

A two-dimensional, two-phase, non-isothermal model was developed for an active, tubular, liquid-feed direct methanol fuel cell (DMFC). The liquid-gas, two-phase mass transport in the porous anode and cathode was formulated based on the multi-fluid approach in the porous media. The two-phase mass transport in the anode and cathode channels was modeled using the drift-flux and the homogeneous mist-flow models, respectively. Water and methanol crossovers through the membrane were considered due to the effects of diffusion, electro-osmotic drag, and convection. The model enabled a numerical investigation of the effects of various operating parameters, such as current density, methanol flow rate, and oxygen flow rate, on the mass and heat transport characteristics in the tubular DMFC. It was shown that by choosing a proper tube radius and distance between the adjacent cells, a tubular DMFC stack can achieve a much higher energy density compared to its planar counterpart. The results also showed that a large anode flow rate is needed in order to avoid severe blockage of liquid methanol to the anode electrode due to the gas accumulation in the channel. Besides, lowering the flow rate of either the methanol solution or air can lead to a temperature increase along the flow channel. The methanol and water crossovers are nearly independent of the methanol flow rate and the air flow rate.