Operation of a direct methanol fuel cell stack by self-heating at low temperatures

The operation characteristics of a direct methanol fuel cell (DMFC) are investigated at low temperatures of −5 °C and −10 °C by using a laboratory-made 10-cell stack. The stack is operated only by heat generation of internal exothermic reactions without any heating device and additional insulation means, to examine behaviors of the stack performance at low temperatures. The self-heating stack is successfully operated in a stable manner at −10 °C by control of the operation modes. An appropriate operation strategy using the fuel switching as well as selection of the operation modes is proposed, and possibility and limitation for operation of DMFC stacks by self-heating under cold conditions are discussed, based on the results.     

Development of a passive direct methanol fuel cell (DMFC) twin-stack for long-term operation

Direct methanol fuel cell (DMFC), with benefits such as high energy efficiency, quick start capability and instantaneous refueling, is a promising power source to meet the ever-increasing power demand for portable electronic products. In this paper, a novel CO₂-driven fuel-feed device was produced and equipped in a passive 8-cell DMFC twin-stack for long-term operation. It was shown that this fuel-feed device was capable of supplying methanol solution continuously in response to the change in discharging current of the stack. Stainless steel sheet was photochemically etched as current collectors based on MEMS techniques. Series interconnections between two neighbor cells were realized in banded configuration which avoided the external connection. TiN-plated mesh was placed between current collector and membrane electrode assembly (MEA), which was used to lessen the internal resistance of the stack. A peak power density of 16.9 mW cm⁻² was achieved with 4 M methanol at ambient temperature and passive operation. The stack equipped with the fuel feed device successfully powered a sensor node for 39 h with the consumption of 80 ml of 4 M methanol.     

Dynamic response and long-term stability of a small direct methanol fuel cell stack

This study examines the operating characteristics and durability of a small direct methanol fuel cell (DMFC) stack (volume: 39.6 cm³). To investigate the operating characteristics in a real multi-user operating mode, various load cycles (such as gradual acceleration and deceleration), two operating modes (current mode or voltage mode) and four interrupted operating methods (load on-off, load-methanol on-off, load-air on-off, and load-methanol-air on-off) are used. The durability of the DMFC stack is examined at a constant voltage of 2.4 V (0.4 V per cell) by using the load-methanol-air on-off mode for more than 2000 h. In these tests, the DMFC stack exhibits a rapid, stable and dynamic response regardless of the load cycle and operating mode, though the stack performance and response behaviour vary with the interrupted operating modes. Among the operating modes, the air-interruption modes exhibit better stability and higher performance. Moreover, the load-methanol-air on-off mode provides the stack with good durability and a high performance in a long-term test of 2045 h.     

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.     

Anionic-cationic bi-cell design for direct methanol fuel cell stack

A new fuel cell stack design is described using an anion exchange membrane (AEM) fuel cell and a proton exchange membrane (PEM) fuel cell in series with a single fuel tank servicing both anodes in a passive direct methanol fuel cell configuration. The anionic-cationic bi-cell stack has alkaline and acid fuel cells in series (twice the voltage), one fuel tank, and simplified water management. The series connection between the two cells involves shorting the cathode of the anionic cell to the anode of the acidic cell. It is shown that these two electrodes are at essentially the same potential which avoids an undesired potential difference and resulting loss in current between the two electrodes. Further, the complimentary direction of water transport in the two kinds of fuel cells simplifies water management at both the anodes and cathodes. The effect of ionomer content on the AEM electrode potential and the activity of methanol oxidation were investigated. The individual performance of AEM and PEM fuel cells were evaluated. The effect of ion-exchange capacity in the alkaline electrodes was studied. A fuel wicking material in the methanol fuel tank was used to provide orientation-independent operation. The open circuit potential of the bi-cell was 1.36 V with 2.0 M methanol fuel and air at room temperature.     

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.     

Operating characteristics and performance stability of 5 W class direct methanol fuel cell stacks with different cathode flow patterns

In this study, 5 W class direct methanol fuel cell (DMFC) stacks using the flow field patterns of serpentine, parallel, and square spot are fabricated to compare how well they are capable of mass transport and water removal in the cathode. The stability of the stack is predicted through the simulation results of the flow field patterns on the pressure drop and the water mass fraction in the cathode of the stack. It is then estimated through the performance and the voltage distribution of the stack. According to the simulation results, although the square spot pattern shows the lowest pressure drop, the square spot pattern has much higher water mass fraction in the central region of the channel compared to the other flow field patterns. In accordance with the results, a square spot pattern for the stack-SSMA exhibits very poor water removal capabilities, leading to water flooding near the channel exit. In contrast, the performance stability of a stack-SPMA is comparable to the stack-SSMM.     

Development of planar air breathing direct methanol fuel cell stacks

In this paper, design criteria and development techniques for planar air breathing direct methanol fuel cell stacks are described in detail. The fuel cell design in this study incorporates a window-frame structure that provides a large open area for more efficient mass transfer and is modular, making it possible to fabricate components separately. The membrane electrode assembly and gas diffusion layers are laminated together to reduce contact resistance, which eliminates the need for heavy hardware. The composite current collector is low cost, has high electrical conductivity and corrosion resistance. In the interest of quick and cost-efficient prototyping, the fabrication techniques were first developed on a single cell with an active area of 1.0 cm². Larger single cells with active areas of 4.5 and 9.0 cm² were fabricated using techniques based on those developed for the smaller single cell. Two four-cell stacks, one with a total active area of 18.0 cm² and the other with 36.0 cm², were fabricated by inter-connecting four identical cells in series. These four-cell stacks are suitable for portable passive power source applications. The performance analysis of single cells as well as stacks is presented. Peak power outputs of 519.0 and 870.0 mW were achieved in the stacks with active areas of 18.0 and 36.0 cm², respectively. The effects of methanol concentration and fuel cell self-heating on the fuel cell performance are emphasized.     

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.     

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 analysis of a passive direct methanol fuel cell

An analytical, one-dimensional, steady state model is employed to solve for overpotentials at the catalyst layers along with the liquid water and methanol distributions at the anode, and oxygen transport at the cathode. An iterative method is utilized to calculate the cell temperature at each cell current density. A comprehensive exergy analysis considering all possible species inside the cell during normal operation is presented. The contributions of different types of irreversibilities including overpotentials at the anode and cathode, methanol crossover, contact resistance, and proton conductivity of the membrane are investigated. Of all losses, overpotentials in conjunction with the methanol crossover are considered as the major exergy destruction sources inside the cell during the normal operation. While the exergy losses due to electrochemical reactions are more significant at higher current densities, exergy destruction by methanol crossover at the cathode plays more important role at lower currents. It is also found that the first-law efficiency of a passive direct methanol fuel cell increases as the methanol solution in the tank increases in concentration from 1 M to 3 M. However, this is not the case with the second-law efficiency which is always decreasing as the concentration of the methanol solution in the tank increases.     

Control of variable power conditions for a membraneless direct methanol fuel cell

The control of a direct methanol fuel cell (DMFC) operating under variable power conditions is important in the development of a commercially applicable device. Fuel cells are conventionally designed for a maximum power output. However variable load cycles can result in fuel cell operation under sub-optimal conditions. In this paper, a simple method of power management using a physical guard is presented. The guard can be used on the anode or cathode electrode, in the membraneless gap or in any combination. This design selectively deactivates specific active regions of the electrode assembly and enables the DMFC to operate at a constant voltage and current density at different absolute power conditions. The guard also serves to control excessive crossover during shutdown and low power operation.     

Development of optimisation model for direct methanol fuel cells via cell integrated network

A cell network consists of a combination of fuel cells to achieve the targeted power consumption for a specific application. The main objective of this study is to design and optimise direct methanol fuel cell (DMFC) via cell integrated network model targeted for small portable application, such as cell phones and tablets. The target current and voltage was 1400 mA and 3.7 V, respectively, for a 5.18 W of cell network power. The optimisation was performed using 16 cells that were arranged in series with a voltage output of 3.781 V and a current of 1400 mA. The overall active area for the cell network was 128 cm², and the cost of 1 set of cell networks is USD 1400.     

Non-isothermal dynamic modelling and optimization of a direct methanol fuel cell

A non-isothermal dynamic optimization model of direct methanol fuel cells (DMFCs) is developed to predict their performance with an effective optimum-operating strategy. After investigating the sensitivities of the transient behaviour (the outlet temperature, crossovers of methanol and water, and cell voltage) to operating conditions (the inlet flow rates into anode and cathode compartments, and feed concentration) through dynamic simulations, we find that anode feed concentration has a significantly larger impact on methanol crossover, temperature, and cell voltage than the anode and cathode flow rates. Also, optimum transient conditions to satisfy the desired fuel efficiency are obtained by dynamic optimization. In the developed model, the significant influence of temperature on DMFC behaviour is described in detail with successful estimation of its model parameters.     

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.     

Development of a direct methanol fuel cell stack fed with pure methanol

Two passive fuel cell stacks with the same four MEAs in a series connection have been fabricated, tested, and compared. The dilute-stack was filled with 30 mL dilute methanol solutions (1–3 M), whereas the pure-stack was driven by 3 mL pure methanol. In the pure-stack, porous components were added on both sides of the MEAs to modify its mass transfer characteristics so that the stack could directly use pure methanol as fuel without having severe methanol crossover. The performance, fuel efficiency, energy efficiency, and electrochemical impedance spectroscopy (EIS) responses of the passive dilute-stack and pure-stack were measured at room temperature with different fuels. The pure-stack using pure methanol showed similar performance with the dilute-stack using 1 M methanol solution. The measured fuel efficiency and energy efficiency of the pure-stack were 53.6% and 13.3%, respectively, at 1.2 V. Since 100% methanol, instead of the less than 10% methanol solutions, was used as fuel, the energy density of the pure-stack per weight of fuel was more than 10 times higher than that of the dilute stack.     

A synthesis of CO-tolerant Nb2O5-promoted Pt/C catalyst for direct methanol fuel cell; its physical and electrochemical characterization

A Pt-Nb₂O₅/C electrocatalyst was synthesized by a two-step process as an anode material in direct methanol fuel cell (DMFC). The Pt-Nb₂O₅/C catalysts heat-treated at different temperatures (400 and 500 °C) in flowing N₂ were characterized by various methods such as inductively coupled plasma-atomic emission spectroscopy, X-ray diffraction, transmission electron microscopy, and X-ray photoemission spectroscopy (XPS). The heat-treated Pt-Nb₂O₅/C catalyst at 400 °C showed the best electrochemical activity for CO and methanol oxidations among the prepared catalysts. The XPS results showed the electronic structure change of Pt, indicating a formation of interaction between Pt and Nb₂O₅. It is suggested that a synergistic effect between Pt and Nb₂O₅ enhances the electrocatalytic activity for CO and methanol oxidations. We believe that Nb₂O₅-promoted Pt/C catalyst may be regarded as one of the attractive candidates as an anode material in DMFC.     

Performance of air-breathing direct methanol fuel cell with anion-exchange membrane

This report details development of an air-breathing direct methanol alkaline fuel cell with an anion-exchange membrane. The commercially available anion-exchange membrane used in the fuel cell was first electrochemically characterized by measuring its ionic conductivity, and showed a promising result of 1.0 × 10⁻¹ S cm⁻¹ in a 5 M KOH solution. A laboratory-scale direct methanol fuel cell using the alkaline membrane was then assembled to demonstrate the feasibility of the system. A high open-circuit voltage of 700 mV was obtained for the air-breathing alkaline membrane direct methanol fuel cell (AMDMFC), a result about 100 mV higher than that obtained for the air-breathing DMFC using a proton exchange membrane. Polarization measurement revealed that the power densities for the AMDMFC are strongly dependent on the methanol concentration and reach a maximum value of 12.8 mW cm⁻² at 0.3 V with a 7 M methanol concentration. A durability test for the air-breathing AMDMFC was performed in chronoamperometry mode (0.3 V), and the decay rate was approximately 0.056 mA cm⁻² h⁻¹ over 160 h of operation. The cell area resistance for the air-breathing AMDMFC was around 1.3 Ω cm² in the open-circuit voltage (OCV) mode and then is stably supported around 0.8 Ω cm² in constant voltage (0.3 V) mode.     

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.     

Design,fabrication and performance analysis of a 200 W PEM fuel cell short stack

A PEM fuel cell short stack of 200 W capacity, with an active area of 100 cm² has been designed and fabricated in-house. The status of unit cell performance was 0.55 W cm⁻². Based on the unit cell technology, a short stack has been developed. The proper design of uniform flow distribution, cooling plate and compressed end plate were important to achieve the best performance of the short stack. The performance of four cells stack was analyzed in static and dynamic modes. In the static mode of polarization curve, the stack has peak power density of 0.55 W cm⁻² (220 W) at 0.5 V per cell, when the voltage was scanning from low to high voltage (1.5–3.5 V), and resulted in minimum water flooding inside the stack. In this study a series of dynamic loadings were tested to simulate the vehicle acceleration. The fuel cell performances respond to dynamic loading influenced by the hydrogen/air stoichiometric, back pressure, and dynamic-loading time. It was needed high hydrogen stoichiometric and back pressure to maintain high dynamic performance. In the long-time stable power testing, the stack was difficult to maintain at high performance, due to the water flooding at high output power. An adjusting cathode back-pressure method for purging water was proposed to prevent the water flooding at flow channels and maintain the stable output power at 170 W (0.42 W cm⁻²).