A semi-empirical model for efficiency evaluation of a direct methanol fuel cell

Energy density and power density are two of the most significant performance indices of a fuel cell system. Both the indices are closely related to the operating conditions. Energy density, which can be derived from fuel cell efficiency, is especially important to small and portable applications. Generally speaking, power density can be easily obtained by acquiring the voltage and current density of an operating fuel cell. However, for a direct methanol fuel cell (DMFC), it is much more difficult to evaluate its efficiency due to fuel crossover and the complex architecture of fuel circulation. The present paper proposes a semi-empirical model for the efficiency evaluation of a DMFC under various operating conditions. The power density and the efficiency of a DMFC are depicted by explicit functions of operating temperature, fuel concentration and current density. It provides a good prediction and a clear insight into the relationship between the aforementioned performance indices and operating variables. Therefore, information including power density, efficiency, as well as remaining run-time about the status of an operating DMFC can be in situ evaluated and predicted. The resulting model can also serve as an important basis for developing real-time control strategies of a DMFC system.     

Nanostructured Pd barrier for low methanol crossover DMFC

This work reports the successful fabrication of Pd nanostructured proton conducting-fluid blocking barriers on standard perfluorosulfonic acid membranes, able to reduce considerably methanol crossover in Direct Methanol Fuel Cells. The barrier nanostructure and grafting to the underlying membrane was optimized by fine-tuning the deposition conditions. A reduction in methanol crossover up to 50% was achieved, increasing significantly the fuel cell efficiency, admitting a slight power density reduction with respect to a reference cell. The developed barriers hindered methanol transport through the membrane as well as water transport, therefore membrane dehydration can be observed at low current density, if operating conditions are not suitably modified.     

Towards operating direct methanol fuel cells with highly concentrated fuel

A significant advantage of direct methanol fuel cells (DMFCs) is the high specific energy of the liquid fuel, making it particularly suitable for portable and mobile applications. Nevertheless, conventional DMFCs have to be operated with excessively diluted methanol solutions to limit methanol crossover and the detrimental consequences. Operation with diluted methanol solutions significantly reduces the specific energy of the power pack and thereby prevents it from competing with advanced batteries. In view of this fact, there exists a need to improve conventional DMFC system designs, including membrane electrode assemblies and the subsystems for supplying/removing reactants/products, so that both the cell performance and the specific energy can be simultaneously maximized. This article provides a comprehensive review of past efforts on the optimization of DMFC systems that operate with concentrated methanol. Based on the discussion of the key issues associated with transport of the reactants/products, the strategies to manage the supply/removal of the reactants/products in DMFC operating with highly concentrated methanol are identified. With these strategies, the possible approaches to achieving the goal of concentrated fuel operation are then proposed. Past efforts in the management of the reactants/products for implementing each of the approaches are also summarized and reviewed.     

Fuel sensor-less control of a liquid feed fuel cell under dynamic loading conditions for portable power sources (II)

This work presents a new fuel sensor-less control scheme for liquid feed fuel cells that is able to control the supply to a fuel cell system for operation under dynamic loading conditions. The control scheme uses cell-operating characteristics, such as potential, current, and power, to regulate the fuel concentration of a liquid feed fuel cell without the need for a fuel concentration sensor. A current integral technique has been developed to calculate the quantity of fuel required at each monitoring cycle, which can be combined with the concentration regulating process to control the fuel supply for stable operation. As verified by systematic experiments, this scheme can effectively control the fuel supply of a liquid feed fuel cell with reduced response time, even under conditions where the membrane electrolyte assembly (MEA) deteriorates gradually. This advance will aid the commercialization of liquid feed fuel cells and make them more adaptable for use in portable and automotive power units such as laptops, e-bikes, and handicap cars.     

Modeling of a passive DMFC operating with neat methanol

A mathematical model is developed to simulate the fundamental transport phenomena in a passive direct methanol fuel cell (DMFC) operating with neat methanol. The neat methanol operation is realized by using a ‘pervaporation’ membrane that allows the methanol concentration from the neat methanol in the fuel reservoir to be declined to an appropriate level in the anode catalyst layer (CL). The water required by the methanol oxidation reaction on the anode is passively obtained by diffusion from the cathode through the membrane. The numerical results indicate that the methanol delivery rate from the fuel reservoir to the anode CL is predominately controlled by the pervaporation process. It is also found that under the neat methanol operating condition, water distribution across the membrane electrode assembly is greatly influenced by the membrane thickness, the cathode design, the operating temperature, and the ambient relative humidity.     

Modelling and experimental studies on a direct methanol fuel cell working under low methanol crossover and high methanol concentrations

A number of issues need to be resolved before DMFC can be commercially viable such as the methanol crossover and water crossover which must be minimised in portable DMFCs.     

Numerical modeling and simulations of active direct methanol fuel cell (DMFC) systems under various ambient temperatures and operating conditions

Direct methanol fuel cells (DMFCs) are potential candidates for portable backup power generation and auxiliary power units owing to their advantageous features, such as ease of fuel storage and delivery. Optimizing each component of a DMFC system is critical to improving the overall system performance and power density. This paper presents an active DMFC system model, in which a one-dimensional DMFC stack model is combined with major system components, including fuel and water tanks, liquid–gas separator, heat exchangers, pumps, and blowers. The model is implemented using a commercial flow-sheet simulator, ASPEN-HYSYS, and then applied to an active DMFC system to analyze the effects of the DMFC operating parameters and heat management. Special emphasis is placed on establishing active control strategies for the DMFC stack temperature, methanol crossover rate, and water recovery by optimizing the system components and operating conditions. Overall, this study helps identify innovative active DMFC system designs and configurations.     

Fuel sensor-less control of a liquid feed fuel cell under dynamic loading conditions for portable power sources (I)

This work presents a novel fuel sensor-less control scheme for a liquid feed fuel cell system that operates under dynamic loading conditions and is suitable for portable power sources. The proposed technique utilizes the operating characteristics of a fuel cell, such as voltage, current and power, to control the supply of liquid fuel and regulate its concentration. As verified by systematic experiments, this scheme controls effectively the supply of fuel under dynamic loading conditions and pushes the system toward higher power output. The primary features and advantages of sensor-less fuel control are as follows. When the fuel concentration sensor is excluded, the cost of a liquid feed fuel cell system is decreased and system volume and weight are reduced, thereby increasing specific energy density and design simplicity, and shortening system response time. Notably, temperature compensation for measurement data is unnecessary. With a decreased number of components, the control scheme improves durability and reliability of liquid feed fuel cells. These advantages will help commercialization of liquid feed fuel cells as portable power sources.     

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.     

Experimental investigation of current distribution in a direct methanol fuel cell with serpentine flow-fields under various operating conditions

The influences of various operating conditions on the current distribution of a direct methanol fuel cell with flow-fields of serpentine channels are investigated by means of a current-mapping method. The current densities generally deviate more from an even distribution when the cell temperature or flow rate of the cathode reactant is lower, or when the current loaded on the cell or the methanol concentration is higher. In addition, uneven current distributions decrease the cell performance. Relevant mass-transfer phenomena such as water flooding and methanol crossover are discussed. The characteristics of the channel configuration also affect the current density profiles. With a five-line serpentine channel, the current densities are lowered periodically where the flow direction is inverted due to the corner flow effect and the subsequent water accumulation. With a single serpentine channel, on the other hand, the current densities peak periodically where the flow direction is inverted due to enhanced air convection through the gas-diffusion layer.     

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 semi-empirical model considering the influence of operating parameters on performance for a direct methanol fuel cell

This research focuses on modeling the relationships between operating parameters and performance measures for a single stack direct methanol fuel cell (DMFC). Four operating parameters, including temperature, methanol concentration, and methanol and air flow rates, are considered in this work. Performance of the DMFC is described by the relationship between current density and voltage. The open circuit voltage and voltage drop in the closed circuit due to resistance, activation, and concentration polarization are influenced by the operating parameters. To consider both modeling accuracy and simplicity, a semi-empirical model is developed in this work by integrating theoretical and approximation models. Experiments were designed and conducted to collect the required data and to obtain the coefficients in the semi-empirical model. The error analysis indicates that our semi-empirical model is effective for predicating the DMFC's performance. The influence of the four operating parameters on the DMFC's performance is also analyzed based on this semi-empirical model. Possible applications of the semi-empirical model in the optimal control of fuel cell systems are also discussed.     

Influences of fuel crossover on cathode performance in a micro borohydride fuel cell

Influences of borohydride crossover on cathode performance were studied in a micro direct borohydride fuel cell (DBFC). The results showed that fuel crossover resulted in decreases in open circuit potentials of cathodes. On the other hand, effects of fuel crossover on cathode overpotentials strongly depended on the cathode material. The Pt/C cathode demonstrated a small potential drop of 0.11 V, while the Ag/C cathode had a much larger potential drop of 0.26 V under the same condition. Fuel crossover was found to be depressed during current operations. It is possible that fuel depletion happened around the anode during operation, resulting in a decrease of fuel concentration gradient across the membrane and thus less crossover. Experiments also showed that a balance in wet-proof property is essential for the cathode in the direct borohydride fuel cell and the stability of cell performance was mainly dependent on wet-proof durability of the cathode.     

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

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

Modeling of dynamic operating behaviors in a liquid-feed direct methanol fuel cell

A transient, two-dimensional two-phase mass transport model is applied to investigate the cell dynamic operating behaviors of a liquid-feed direct methanol fuel cell (DMFC). The influences of various processes on the cell dynamics in response to sudden change of cell current density, methanol feed concentration, oxygen feed concentration, and the transient gas-slug blocking in the anode channel are studied. The results reveal that in response to the sudden drop of cell current density and methanol concentration, the cell voltage exhibits overshooting behavior as a result of the interaction between cathode and anode overpotentials with different time responses. The dominant factor causing the long response of cell voltages is the methanol rebalance in the membrane electrode assembly, which usually takes tens of seconds because of the sluggish methanol transport process. Also, it is indicated that in response to temporary blocking of anode diffusion layer surface with gas slug, the cell can still operate normally for a while because the anode diffusion layer serves as the fuel reservoir. It takes over a minute for the cell to break down in this case studied, implying that the cell output can be maintained stable if the gas bubbles or slugs in the anode channel can be removed quickly. However, too long residence time of gas slug in the channel definitely degrades the cell performance.     

Mass balance research for high electrochemical performance direct methanol fuel cells with reduced methanol crossover at various operating conditions

Mass balance research in direct methanol fuel cells (DMFCs) provides a more practical method in characterizing the mass transport phenomena in a membrane electrode assembly (MEA). This method can be used to measure methanol utilization efficiency, water transport coefficient (WTC), and methanol to electricity conversion rate of a MEA in DMFCs. First, the vital design parameters of a MEA are recognized for achieving high methanol utilization efficiency with increased power density. In particular, the structural adjustment of anode diffusion layer by adding microporous layer (MPL) is a very effective way to decrease WTC with reduced methanol crossover due to the mass transfer limitation in the anode. On the other hand, the cathode MPL in the MEA design can contribute in decreasing methanol crossover. The change of structure of cathode diffusion layer is also found to be a very effective way in improving power density. In contrast, the WTC of DMFC MEAs remains virtually constant in the range of 3.4 and 3.6 irrespective of the change of the cathode GDL. The influence of operating condition on the methanol utilization efficiency, WTC, and methanol to electricity conversion rate is also presented and it is found that these mass balance properties are strongly affected by temperature, current density, methanol concentration, and the stoichiometry of fuel and air.     

Experimental measurements of fuel and water crossover in an active DMFC

This study measured polarization curves as well as the high-frequency resistance of active direct methanol fuel cell (DMFC) operates at around 80 °C with active controls of temperature, methanol concentration, airflow rate, and relative humidity. The relative humidity of the air did not have noticeable impacts on the fuel cell unless the operating temperature was near the evaporation temperature of water (100 °C). The hydrophobic water management layer (WML) between the membrane electrode assembly (MEA) and cathode air channel increases the mass transfer resistance and improves the water retention in MEA. Adding a WML increased the peak power density, decreased the ohmic resistance, and improved the fuel efficiency of the fuel cell, especially when it operated near 100 °C. This study also quantitatively measured methanol and water crossover as well as the fuel efficiency at different operating currents. The fuel efficiency increased significantly with the increase of the current density. Using a hydrophobic fuel management layer (FML) between the anode fuel channel and MEA reduced the fuel and water crossover rates and increased the ohmic resistance due to the decrease of the water content of the Nafion membrane. The FML improved fuel efficiency by reducing the methanol crossover. The combination of the FML and WML enabled the steady operation of DMFC using highly concentrated methanol solutions (up to 75 wt%).     

An algorithm for sensor-less fuel control of direct methanol fuel cells

We report an algorithm for real-time control of the fuel of a DMFC. The MEA voltage decay coefficients [e₁, e₂], and I-V-T, M′-I-T, and W′-I-T curves (where I is the current, V the voltage, T the temperature, and M′ and W′ the methanol and water consumption rates, respectively) of n fuels with specified methanol concentrations C_M,k (k = 1, 2,…, n) are pre-established and form (I,V,T), (M′,I,T), and (W′,I,T) surfaces for each C_M,k. The in situ measured (I,V,T)_u after voltage decay correction is applied to the n preset (I,V,T) surfaces to estimate C_M,u (the C_M corresponding to (I,V,T)_u) using an interpolation procedure. The C_M,u is then applied to the n preset (M′,I,T) and (W′,I,T) surfaces to estimate cumulated “methanol” and “water” consumed quantities . Thus in a real-time system, the C_M and total quantity of fuel can be controlled using the estimated C_M,u and cumulated “methanol” and “water” consumed quantities.     

Optimization of fuel cell system operating conditions for fuel cell vehicles

Proton exchange membrane fuel cell (PEMFC) technology for use in fuel cell vehicles and other applications has been intensively developed in recent decades. Besides the fuel cell stack, air and fuel control and thermal and water management are major challenges in the development of the fuel cell for vehicle applications. The air supply system can have a major impact on overall system efficiency. In this paper a fuel cell system model for optimizing system operating conditions was developed which includes the transient dynamics of the air system with varying back pressure. Compared to the conventional fixed back pressure operation, the optimal operation discussed in this paper can achieve higher system efficiency over the full load range. Finally, the model is applied as part of a dynamic forward-looking vehicle model of a load-following direct hydrogen fuel cell vehicle to explore the energy economy optimization potential of fuel cell vehicles.     

Exergy flow and energy utilization of direct methanol fuel cells based on a mathematic model

An exergetic analysis model for direct methanol fuel cell (DMFC) is established in the present paper. Expressions of electrical, thermal and total exergetic efficiencies have been deduced with consideration of methanol crossover and over potential in operation. Furthermore, energy utilization of a DMFC system is quantitatively calculated and changes of electrical efficiency and thermal efficiency at various current density, methanol concentration, operating temperature, and cathode pressure have been investigated. Some suggestions of optimal operating conditions of direct methanol fuel cell based on our findings are put forward. Results show that the thermal energy generated in a DMFC takes up a significant amount of exergy in total energy and should be sufficiently used to obtain high total efficiency in a DMFC, high methanol crossover rate is the predominant cause of energy loss when the fuel cell operates at low current density, and total exergetic efficiency of a DMFC reaches its peak value at relatively high current density.