Performance characteristics of a novel tubular-shaped passive direct methanol fuel cell

The present work consists of a tubular-shaped direct methanol fuel cell (DMFC) that is operated completely passively with methanol solution stored in a central fuel reservoir. The benefit of a tubular-shaped DMFC over a planar-shaped DMFC is the higher instantaneous volumetric power energy density (power/volume) associated with the larger active area provided by the tubular geometry. Membrane electrode assemblies (MEAs) with identical compositions were installed in both tubular and planar-shaped, passive DMFCs and tested with 1, 2, and 3 M methanol solutions at room temperature. The peak power density for the tubular DMFC was 19.0 mW cm⁻² and 24.5 mW cm⁻² while the peak power density for the planar DMFC was 20.0 mW cm⁻² and 23.0 mW cm⁻² with Nafion^® 212 and 115 MEAs, respectively. Even though the performance of the fuel cell improved with each increase in methanol concentration, the fuel and energy efficiencies decreased for both the tubular and planar geometries due to increased methanol crossover. The tubular DMFC experienced higher methanol crossover potentially due to a higher static fluid pressure in the anode fuel reservoir (AFR) caused by the vertical orientation of the tubular fuel reservoir. The performance of the tubular DMFC in this work represents an 870% improvement in power density from the previous best, passive, tubular DMFC found in the literature.     

Fabrication and evaluation of a passive alkaline membrane micro direct methanol fuel cell

A passive silicon microfabricated direct methanol fuel cell employing a polymer anion exchange membrane has been identified as a promising integrable power supply for portable devices in the MEMS field. In this work the fabrication steps of the different components: silicon current collectors and membrane-electrode assembly (MEA), as well as the mounting approach and performance evaluation for the whole passive alkaline micro air-breathing direct methanol fuel cell (μADMFC) are shown. This system, with a small active area of 0.25 cm², was tested near of the real application conditions with totally passive fueling and at room temperature. Different MEA configurations and methanol and KOH concentrations were compared. Best performance was observed for the MEA with a previously sprayed catalytic layer on carbon cloth instead of the MEAs with the catalytic layer deposited directly onto the alkaline membrane. A maximum power density of 2.2 mW cm⁻² was achieved for 15 μL of 1 M methanol + 4 M KOH fuel solution.     

Development of a 1 W passive DMFC

In this paper, development techniques for a passive DMFC prototype in the 1 W range are described in detail. The prototype includes a fuel cell stack, a fuel tank and a passive ancillary system (termed “thermal-fluids management system” in this paper). The fuel cell stack in this study incorporates a window-frame structure that provides a large open area for more efficient mass transfer and is modular. Two stack units connected in series, with a total combined active area of 72.0 cm², are used in the prototype. The thermal-fluids management system utilizes passive approaches for fuel storage and delivery, air-breathing, water management, CO₂ release, and thermal management. The air filter also serves as a waterproof layer for the cathode in order to prevent water contamination. Water immersion tests are conducted to evaluate the air filter. The performance evaluation of the prototype is performed in two fuel feeding modes: dilute methanol solution and pure methanol. A peak power output of 1.5 W is achieved with the dilute methanol solution feed.     

Portable DMFC system with methanol sensor-less control

This work develops a prototype 20 W portable DMFC by system integration of stack, condenser, methanol sensor-less control and start-up characteristics. The effects of these key components and control schemes on the performance are also discussed. To expedite the use of portable DMFC in electronic applications, the system utilizes a novel methanol sensor-less control method, providing improved fuel efficiency, durability, miniaturization and cost reduction. The operating characteristics of the DMFC stack are applied to control the fuel ejection time and period, enabling the system to continue operating even when the MEAs of the stack are deteriorated. The portable system is also designed with several features including water balance and quick start-up (in 5 min). Notably, the proposed system using methanol sensor-less control with injection of pure methanol can power the DVD player and notebook PC. The system specific energy and energy density following three days of operation are 362 Wh kg⁻¹ and 335 Wh L⁻¹, respectively, which are better than those of lithium batteries (∼150 Wh kg⁻¹ and ∼250 Wh L⁻). This good energy storage feature demonstrates that the portable DMFC is likely to be valuable in computer, communication and consumer electronic (3C) markets.     

Passive direct methanol fuel cells fed with methanol vapor

A vapor fed passive direct methanol fuel cell (DMFC) is proposed to achieve a high energy density by using pure methanol for mobile applications. Vapor is provided from a methanol reservoir to the membrane electrode assembly (MEA) through a vaporizer, barrier and buffer layer. With a composite membrane of lower methanol cross-over and diffusion layers of hydrophilic nanomaterials, the humidity of the MEA was enhanced by water back diffusion from the cathode to the anode through the membrane in these passive DMFCs. The humidity in the MEA due to water back diffusion results in the supply of water for an anodic electrochemical reaction with a low membrane resistance. The vapor fed passive DMFC with humidified MEA maintained 20–25 mW cm⁻² power density for 360 h and performed with a 70% higher fuel efficiency and 1.5 times higher energy density when compared with a liquid fed passive DMFC.     

Behavioral pattern of a monopolar passive direct methanol fuel cell stack

A passive, air-breathing, monopolar, liquid feed direct methanol fuel cell (DMFC) stack consisting of six unit cells with no external pump, fan or auxiliary devices to feed the reactants has been designed and fabricated for its possible employment as a portable power source. The configurations of the stack of monopolar passive feed DMFCs are different from those of bipolar active feed DMFCs and therefore its operational characteristics completely vary from the active ones. Our present investigation primarily focuses on understanding the unique behavioral patterns of monopolar stack under the influence of certain operating conditions, such as temperature, methanol concentration and reactants feeding methods. With passive reactants supply, the temperature of the stack and open circuit voltage (OCV) undergo changes over time due to a decrease in concentration of methanol in the reservoir as the reaction proceeds. Variations in performance and temperature of the stack are mainly influenced by the concentration of methanol. Continuous operation of the passive stack is influenced by the supply of methanol rather than air supply or water accumulation at the cathode. The monopolar stack made up of six unit cells exhibits a total power of 1000 mW (37 mW cm⁻²) with 4 M methanol under ambient conditions.     

A small mono-polar direct methanol fuel cell stack with passive operation

A passive direct methanol fuel cell (DMFC) stack that consists of six unit cells was designed, fabricated, and tested. The stack was tested with different methanol concentrations under ambient conditions. It was found that the stack performance increased when the methanol concentration inside the fuel tank was increased from 2.0 to 6.0 M. The improved performance is primarily due to the increased cell temperature as a result of the exothermic reaction between the permeated methanol and oxygen on the cathode. Moreover, the increased cell temperature enhanced the water evaporation rate on the air-breathing cathode, which significantly reduced water flooding on the cathode and further improved the stack performance. This passive DMFC stack, providing 350 mW at 1.8 V, was successfully applied to power a seagull display kit. The seagull display kit can continuously run for about 4 h on a single charge of 25 cm³ 4.0-M methanol solution.     

Water management of the DMFC passively fed with a high-concentration methanol solution

The methanol barrier layer adopted for high-concentration direct methanol fuel cells (HC-DMFCs) increases water transport resistance, and makes water management in HC-DMFCs more challenging and critical than that in the conventional direct methanol fuel cell (DMFC) without a methanol barrier layer. In the semi-passive HC-DMFC used in this work, oxygen was actively supplied to the cathode side while various concentrated methanol solutions, 4 M, 8 M, 16 M, and neat methanol, were passively supplied from the anode fuel reservoir. The effects of the cathode relative humidity, cathode pressure, and oxygen flow rate on the water crossover coefficient, fuel efficiency, and overall performance of the fuel cell were studied. Results showed that electrolyte membrane resistance, which was determined by its water content, was the predominant factor that determined the performance of a HC-DMFC, especially at a high current density. A negative water crossover coefficient, which indicated that water flowed back from the cathode through the electrolyte membrane to the anode, was measured when the methanol concentration was 8 M or higher. The back flow of water from the cathode is a very important water supply source to hydrate the electrolyte membrane. The water crossover coefficient was decreased by increasing the cathode relative humidity and back pressure. Water flooding at the cathode was not severe in the HC-DMFC, and a low oxygen flow rate was preferred to decrease water loss and yield a better performance. The peak power density generated from the HC-DMFC fed with 16 M methanol solution was 75.9 mW cm⁻² at 70 °C.     

Influence of anion ionomer content and silver cathode catalyst on the performance of alkaline membrane electrode assemblies (MEAs) for direct methanol fuel cells (DMFCs)

Alkaline membrane electrode assemblies (MEAs) were fabricated by a dry spraying method in order to evaluate and improve their performance. I–V tests indicated that the performance of alkaline direct methanol fuel cells (DMFCs) deeply depends on the ionomer contents of MEAs. MEA with 45.4% mass ionomer content showed the highest performance when non-alkaline (MeOH (1 M)) and alkaline (MeOH (1 M), NaOH (0.5 M)) fuels were used. When alkaline fuel was used, the anode and cathode performances of MEAs were also measured. The ionomer content has been shown to contribute ohmic polarization of the anode and diffusion polarization of the cathode. Furthermore, the performance of MEA with an Ag cathode catalyst was characterized. The Ag cathode catalyst was demonstrated to be a promising alternative to a Pt cathode catalyst because of its tolerance for methanol crossover.     

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.     

Metal membrane-type 25-kW methanol fuel processor for fuel-cell hybrid vehicle

A 25-kW on-board methanol fuel processor has been developed. It consists of a methanol steam reformer, which converts methanol to hydrogen-rich gas mixture, and two metal membrane modules, which clean-up the gas mixture to high-purity hydrogen. It produces hydrogen at rates up to 25 N m³/h and the purity of the product hydrogen is over 99.9995% with a CO content of less than 1 ppm. In this fuel processor, the operating condition of the reformer and the metal membrane modules is nearly the same, so that operation is simple and the overall system construction is compact by eliminating the extensive temperature control of the intermediate gas streams. The recovery of hydrogen in the metal membrane units is maintained at 70–75% by the control of the pressure in the system, and the remaining 25–30% hydrogen is recycled to a catalytic combustion zone to supply heat for the methanol steam-reforming reaction. The thermal efficiency of the fuel processor is about 75% and the inlet air pressure is as low as 4 psi. The fuel processor is currently being integrated with 25-kW polymer electrolyte membrane fuel-cell (PEMFC) stack developed by the Hyundai Motor Company. The stack exhibits the same performance as those with pure hydrogen, which proves that the maximum power output as well as the minimum stack degradation is possible with this fuel processor. This fuel-cell ‘engine’ is to be installed in a hybrid passenger vehicle for road testing.     

Development and characteristics of a 400 W-class direct methanol fuel cell stack

In this study, a 400 W-class direct methanol fuel cell (DMFC) stack is developed for large size portable applications and its operating behaviors under the various conditions are monitored. The DMFC stack comprising of 42-cells is assembled with graphite bipolar plates and membrane–electrode assemblies (MEAs) having an active area of 138 cm² per each. The stack is operated by varying the concentrations of methanol, stoichiometry (λ), and the electric load. In addition, other associated factors, such as voltage and temperature distributions along the individual unit cells, pressure drops inside the stack, voltage behaviors in response to the dynamic change of the electric load and the pHs of the effluent solutions from the outlets of both electrodes, are also studied in a detailed manner. The stack produces a power of 400 W under an operating condition of feeding 0.8 M methanol and 34 l/min air at 1 atm, and uniform distributions of temperature and voltage prevail in all the 42 unit cells. A long-term operation coupled with performance restoration processes shows that a typical single cell used in this stack is able to run with a good stability for more than 500 h without any substantial degradation in the performance.     

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.     

Development of a passive direct methanol fuel cell stack for high methanol concentration

In order to develop a vertically arranged passive DMFC with a porous carbon plate, PCP, the effect of the head height of the methanol solution in contact with the porous carbon plate on the power generation was investigated for a 55 mm height using a single cell. The single cell was operated at several methanol concentrations greater than 70 wt%. By filling the reservoir with 90 and 100 wt% methanol solutions, power densities greater than 30 mW cm⁻² for over 10 h were demonstrated. Based on the result of the single cell study, a passive DMFC stack consisting of 8 unit cells with the PCP was designed and fabricated. The power generation characteristics were then experimentally measured. The maximum power output of 1.8 W, which was almost 10% lower than that expected from the single cell performance, was obtained with 100% methanol. At the same time, a nonuniform cell voltage among the 8 unit cells was found as a reason for the decreasing power output with the increasing current.     

Modelling of an HTPEM-based micro-combined heat and power fuel cell system with methanol

A fuel cell-based combined heat and power system using a high temperature proton exchange membrane fuel cell has been modelled. The fuel cell is fed with the outlet hydrogen stream from a methanol steam reforming reactor. In order to provide the necessary heat to this reactor, it was considered the use of a catalytic combustor fed with methanol. The modelling aims to fit the hydrogen production to the demand of the fuel cell to provide 1 kW_e, maintaining a CO concentration always lower than 30,000 ppm. A system with 65 cells (45.16 cm² cell area) stack operating at 150 °C and hydrogen utilization factor = 0.9 (with O₂/methanol ratio = 2 at combustor; H₂O/methanol ratio = 2 and temperature = 300 °C at reformer) needed a total methanol flow of 23.8 mol h⁻¹ (0.96 L h⁻¹) to reach 1 kW_e, with a system power efficiency (LHV basis) ca. 24% and a CHP efficiency over 87%. The ability to recycle the non-converted hydrogen from the fuel cell anode to the combustor and to use the heat produced at the fuel cell for obtaining hot water increased the global energy efficiency.     

Single passive direct methanol fuel cell supplied with pure methanol

A new single passive direct methanol fuel cell (DMFC) supplied with pure methanol is designed, assembled and tested using a pervaporation membrane (PM) to control the methanol transport. The effect of the PM size on the fuel cell performances and the constant current discharge of the fuel cell with one-fueling are studied. The results show that the fuel cell with PM 9 cm² can yield a maximum power density of about 21 mW cm⁻², and a stable performances at a discharge current of 100 mA can last about 45 h. Compared with DMFC supplied with 3 M methanol solution, the energy density provided by this new DMFC has increased about 6 times.     

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.     

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.     

Effect of membrane thickness on the performance and efficiency of passive direct methanol fuel cells

The use of various Nafion membranes, including Nafion 117, 115 and 112 with respective thicknesses of 175 μm, 125 μm and 50 μm, in a passive direct methanol fuel cell (DMFC) was investigated experimentally. The results show that when the passive DMFC operated with a lower methanol concentration (2.0 M), a thicker membrane led to better performance at lower current densities, but exhibited lower performance at higher current densities. When the methanol concentration was increased to 4.0 M, however, the three membranes exhibited similar cell voltages over a wide range of current densities. In contrast, this work also shows the polarization behaviors in an active DMFC when the three membranes were substantially different. Finally, the test of fuel utilization indicates that the passive DMFC with a thicker membrane exhibited higher efficiency.     

The function of hydrophobic cathodic backing layers for high energy passive direct methanol fuel cell

Homemade wet-proofing carbon papers with back-flow effect were applied as backing layers in the cathode of passive air-breathing direct methanol fuel cell (DMFC) fed by pure methanol. With the increase of polytetrafluoroethylene (PTFE) content, the carbon papers exhibited different water transport resistance and generated different back-flow effects. Moreover, PTFE-treated carbon papers were observed by scanning electronic microscope (SEM) to investigate the function of the cross-linked microstructure. Maximum energy density (438 Wh L⁻¹) of the improved pure methanol DMFC was obtained by using carbon paper with 40 wt.% PTFE content as the cathodic backing layer. This value was 6 times larger than that of the conventional DMFC fed by 2 M methanol solution.