The mass transport based on convection effects in a passive DMFC under open-circuit conditions

The study investigates the open-circuit characteristics of a passive direct methanol fuel cell (DMFC) based on temperature-induced convection effects, including the reactants distributions at anode, the non-uniform temperature distribution and the methanol crossover. A two-dimensional, well-thought-out numerical model coupling with mass transfer and momentum transfer is exploited for DMFC to investigate its inner component and temperature distributions under open-circuit condition. In addition, a 4.0 cm² passive DMFC has been designed and manufactured by the laser-cutting technology for experimental verification. The average methanol crossover flux, methanol diffusion coefficient and crossover current are obtained, which coincide with the simulation data well. The temperature-induced convection simulation results show that the distorted temperature distribution becomes more obvious with higher methanol concentration. Furthermore, the polarization curve, cell temperature and open-circuit voltage (OCV) are measured by varying the methanol concentration to conduct more in-depth research on DMFC performance at open circuit state. The results indicate that the temperature is increased, whereas the OCV is decreased with the increase of methanol concentration, accompanied by the phenomenon of methanol crossover is aggravated. The paper provides the theory basis and the optimal operating parameters for safe start-up of DMFC.     

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.     

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.     

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.     

A self-regulated passive fuel-feed system for passive direct methanol fuel cells

Operating a passive direct methanol fuel cell (DMFC) with high methanol concentration is desired because this increases the energy density of the fuel cell system and hence results in a longer runtime. However, the increase in methanol concentration is limited by the adverse effect of methanol crossover in the conventional design. To overcome this problem, we propose a new self-regulated passive fuel-feed system that not only enables the passive DMFC to operate with high-concentration methanol solution without serious methanol crossover, but also allows a self-regulation of the feed rate of methanol solution in response to discharging current. The experimental results showed that with this fuel-feed system, the fuel cell fed with high methanol concentration of 12.0 M yielded the same performance as that of the conventional DMFC running with 4.0 M methanol solution. Moreover, as a result of the increased energy density, the runtime of the cell with this new system was as long as 10.1 h, doubling that of the conventional design (4.4 h) at a given fuel tank volume. It was also demonstrated that this passive fuel-feed system could successfully self-regulate the fuel-feed rate in response to the change in discharging currents.     

An impedance study of an operating direct methanol fuel cell

An electrochemical impedance spectroscopy (EIS) technique was developed to characterize a direct methanol fuel cell (DMFC) under various operating conditions. A silver/silver chloride electrode was used as an external reference electrode to probe the anode and cathode during fuel cell operation and the results were compared to the conventional anode or cathode half-cell performance measurement using a hydrogen electrode as both the counter and reference electrode. The external reference was sensitive to the anode and the cathode as current was passed in a working DMFC. The impedance spectra and DMFC polarization curves were systematically investigated as a function of air and methanol flow rates, methanol concentration, temperature, and current density. Water flooding in the cathode was also examined.     

Effect of cell orientation on the performance of passive direct methanol fuel cells

A passive liquid feed direct methanol fuel cell (DMFC) with neither liquid pump nor a gas compressor was tested at different orientations. The experimental results showed that the vertical operation always yielded better performance than did the horizontal operation. It was further demonstrated that the improved performance in the vertical orientation was caused by the increased operating temperature as a result of a higher rate of methanol crossover, which resulted from the stronger natural convection in the vertical orientation. The constant current discharging tests showed that, although the vertical operation of the passive DMFC can yield better performance, the fuel utilization at this orientation is lower as a result of the increased rate of methanol crossover. It was also shown that the horizontal orientation with the anode facing upward rendered an effective removal of both CO₂ bubbles on the anode and liquid water on the cathode and thereby a relative stable operation. Finally, it was revealed that the horizontal orientation with the anode facing downward exhibited rather unstable and short discharging duration because of the difficulties in removing CO₂ bubbles from the anode and the liquid water from the cathode at this particular orientation.     

Study on operational aspects of a passive direct methanol fuel cell incorporating an anodic methanol barrier

This paper presents an investigation concerning the effects of operating conditions on the performance of a passive direct methanol fuel cell (DMFC). A self-developed porous metal fiber sintered plate (PMFSP) is used as the methanol barrier between the fuel reservoir and current collector at the anode in order to alleviate the effect of methanol crossover. The effectiveness of using this method is validated. A series of operating conditions such as operating orientation, methanol concentration, ambient temperature, forced air convection and dynamic load are evaluated. Results show that the use of a PMFSP promotes a higher cell performance during vertical operation than horizontal orientation. The effect of methanol concentration depends on the PMFSP porosity. A relatively lower porosity is favorable for high-concentration operation. The cell performance gets improved when increasing the ambient temperature and adopting forced air supply at the cathode. Compared with the traditional structure, the use of a PMFSP makes the fuel cell insensitive to the change of blowing intensity. In addition, the dynamic characteristics of the PMFSP-based passive DMFC are also reported.     

空气抽吸式甲醇燃料电池传热与传质特性

空气抽吸式直接甲醇燃料电池不仅具有被动式燃料电池的优点,同时又便于将其串联成电堆提高输出电压。建立以阴极为管道抽吸式结构的直接甲醇燃料电池的三维、两相、非等温稳态数值模型,研究了质子交换膜性能、供给甲醇浓度以及电堆规模对电池性能及燃料利用率的影响。对于保温较好的大电堆,采用低甲醇穿透的改性质子交换膜能同时提升燃料利用率和比功率;此类电堆若采用穿透率低的改性膜,则2 mol/L的甲醇浓度就能保证电池在较大的电流密度区间内维持较高的功率与效率。作为影响电池运行温度的重要因素,电堆规模的大小将直接影响质子交换膜种类与甲醇浓度等关键参数的设计与选择。     

Operational characteristics of the direct methanol fuel cell stack on fuel and energy efficiency with performance and stability

This paper is presented to investigate operational characteristics of a direct methanol fuel cell (DMFC) stack with regard to fuel and energy efficiency, including its performance and stability under various operating conditions. Fuel efficiency of the DMFC stack is strongly dependent on fuel concentration, working temperature, current density, and anode channel configuration in the bipolar plates and noticeably increases due to the reduced methanol crossover through the membrane, as the current density increases and the methanol concentration, anode channel depth, and temperature decreases. It is, however, revealed that the energy efficiency of the DMFC stack is not always improved with increased fuel efficiency, since the reduced methanol crossover does not always indicate an increase in the power of the DMFC stack. Further, a lower methanol concentration and temperature sacrifice the power and operational stability of the stack with the large difference of cell voltages, even though the stack shows more than 90% of fuel efficiency in this operating condition. The energy efficiency is therefore a more important characteristic to find optimal operating conditions in the DMFC stack than fuel efficiency based on the methanol utilization and crossover, since it considers both fuel efficiency and cell electrical power. These efforts may contribute to commercialization of the highly efficient DMFC system, through reduction of the loss of energy and fuel.     

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.     

Improving the water management and cell performance for the passive vapor-feed DMFC fed with neat methanol

A passive vapor-feed direct methanol fuel cell (DMFC) was experimentally investigated to improve its water management and cell performance when neat methanol was directly used. The effects of different water management approaches, including the addition of a water management layer (WML) and a hydrophobic air filter layer (AFL), and the use of thinner membrane on the cell performance, internal resistance, and fuel efficiency were investigated. The transient discharging behavior and long-term stability of the passive vapor-feed DMFC with the optimized water management were also studied. The results showed that by adding a WML and an AFL, or thinning the membrane thickness, the water management capability can be highly improved, not only enhancing the water recovery from the cathode to the anode, leading to a lower internal resistance and better cell performance, but also curbing the methanol crossover, increasing the fuel efficiency. It is also seen from the long-term constant-voltage test that the discharged current varied with the methanol concentration in the tank and the ambient temperature, while no evident permanent performance degradation was encountered after the 150 h test.     

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.     

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.     

Lightweight current collector based on printed-circuit-board technology and its structural effects on the passive air-breathing direct methanol fuel cell

To realize lightweight design of the fuel cell system is a critical issue before it is put into practical use. The printed-circuit-board (PCB) technology can be potentially used for production of current collectors or flow distributors. This study develops prototypes of a single passive air-breathing direct methanol fuel cell (DMFC) and also an 8-cell mono-polar DMFC stack based on PCB current collectors. The effects of diverse structural and operational factors on the cell performance are explored. Results show that the methanol concentration of 6 M promotes a higher cell performance with a peak power density of 18.3 mW cm⁻². The combination of current collectors using a relatively higher anode open ratio and inversely a lower cathode open ratio helps enhance the cell performance. Dynamic tests are also conducted to reveal transient behaviors and its dependence on the operating conditions. To validate the real working status of the DMFC stack, it is coupled with an LED lightening system. The performance of this hybrid system is also reported in this study.     

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.     

基于ROLS算法的RBF神经网络燃料电池电特性建模

提出了一种基于ROLS算法的RBF神经网络辨识建立直接甲醇燃料电池(DMFC)电特性模型的新方法。以电池的工作温度为输入量,电池的电压／电流密度为输出量,利用1200组实验数据作为训练和测试样本,建立了在不同工作温度下,电池的电压／电流密度动态响应模型,仿真结果表明采用RBF神经网络辨识建模的方法是有效的,建立的模型精度较高。     

Effect of operating conditions on water management of membrane electrode assembly for direct methanol fuel cell

介绍了直接甲醇燃料电池(DMFCs)膜电极的水平衡研究对单电池性能和稳定性的影响,研究了电池操作温度,空气流量及电流密度等操作条件对膜电极水平衡的影响.通过调节操作条件改变净水传输系数,进一步表征膜电极水平衡对电池稳定性的影响.结果表明,单电池在60 ℃,阴极常压空气80 mL/min进料,100 mA/cm²条件下工作具有较好的水平衡,最后,测试了单电池在该条件下的稳定性,测试结果表明电池稳定运行200 h后,性能没有明显衰减.     

1D modeling of a flowing electrolyte-direct methanol fuel cell

In this study, the performance characteristics of a flowing electrolyte-direct methanol fuel cell (FE-DMFC) and a direct methanol fuel cell (DMFC) are evaluated by computer simulations; and results are compared to experimental data found in the literature. Simulations are carried out to assess the effects of the operating parameters on the output parameters; namely, methanol concentration distribution, cell voltage, power density, and electrical efficiency of the cell. The operating parameters studied include the electrolyte flow rate, flowing electrolyte channel thickness, and methanol concentration at the feed stream. In addition, the effect of the circulation of the flowing electrolyte channel outlet stream on the performance is discussed. The results show that the maximum power densities that could be achieved do not significantly differ between these two fuel cells; however the electrical efficiency could be increased by 57% when FE-DMFC is used instead of DMFC.     

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.