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.     

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.     

A study on the overall efficiency of direct methanol fuel cell by methanol crossover current

This paper was presented to determine the methanol crossover and efficiency of a direct methanol fuel cell (DMFC) under various operating conditions such as cell temperature, methanol concentration, methanol flow rate, cathode flow rate, and cathode backpressure. The methanol crossover measurements were performed by measuring crossover current density at an open circuit using humidified nitrogen instead of air at the cathode and applied voltage with a power supply. The membrane electrode assembly (MEA) with an active area of 5 cm² was composed of a Nafion 117 membrane, a Pt–Ru (4 mg/cm²) anode catalyst, and a Pt (4 mg/cm²) cathode catalyst. It was shown that methanol crossover increased by increasing cell temperature, methanol concentration, methanol flow rate, cathode flow rate and decreasing cathode backpressure. Also, it was revealed that the efficiency of the DMFC was closely related with methanol crossover, and significantly improved as the cell temperature and cathode backpressure increased and methanol concentration decreased.     

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.     

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.     

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.     

Sensor-less control of methanol concentration based on estimation of methanol consumption rates for direct methanol fuel cell systems

Adequate control over the concentration of methanol is critically needed in operating direct methanol fuel cell (DMFC) systems, because performance and energy efficiency of the systems are primarily dependent on the concentration of methanol feed. For this purpose, we have built a sensor-less control logic that can operate based on the estimation of the rates of methanol consumption in a DMFC. The rates of methanol consumption are measured in a cell and the resulting data are fed as an input to the control program to calculate the amount of methanol required to maintain the concentration of methanol at a set value under the given operating conditions of a cell. The sensor-less control has been applied to a DMFC system employed with a large-size single cell and the concentration of methanol is found to be controlled stably to target concentrations even though there are some deviations from the target values.     

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.     

Systematic approach for modeling methanol mass transport on the anode side of direct methanol fuel cells

A systematic method for modeling direct methanol fuel cells, with a focus on the anode side of the system, is advanced for the purpose of quantifying the methanol crossover phenomenon and predicting the concentration of methanol in the anode catalyst layer of a direct methanol fuel cell. The model accounts for fundamental mass transfer phenomena at steady state, including convective transport in the anode flow channel, as well as diffusion and electro-osmotic drag transport across the polymer electrolyte membrane. Experimental measurements of methanol crossover current density are used to identify five modeling parameters according to a systematic parameter estimation methodology. A validation study shows that the model matches the experimental data well, and the usefulness of the model is illustrated through the analysis of effects such as the choice fuel flow rate in the anode flow channel and the presence of carbon-dioxide bubbles.     

Effects of structural aspects on the performance of a passive air-breathing direct methanol fuel cell

This study systematically investigates the effects of structural aspects on the performance of a passive air-breathing direct methanol fuel cell (DMFC). Three factors are selected in this study: (1) two different open ratios of the current collector; (2) two different assembly methods of the diffusion layer; and (3) three membrane types with different thicknesses. The interrelations and interactions among these factors have been taken into account. The results demonstrate that these structural factors combine to significantly affect the cell performance of DMFCs. The higher open ratio not only provides a larger area for mass transfer passage and facilitates removal of the products, but also promotes higher methanol crossover. The hot-pressed diffusion layer (DL) can mitigate methanol permeation while the non-bonded variant is able to enhance product removal. The increase of membrane thickness helps obtain a lower methanol crossover rate and higher methanol utilisation efficiency, but also depresses cell performance under certain conditions. In this research, the maximum power density of 10.7 mW cm⁻² is obtained by selecting the current collector with a lower open ratio, the non-bonded DL, and the Nafion 117 membrane. The effect of methanol concentration on the performance of DMFCs is also explored.     

Direct methanol fuel cell performance of sulfonated polyimide membranes

Sulfonated polyimides (SPIs) derived from 1,4,5,8-naphthalene tetracarboxylic dianhydride, 4,4′-bis(4-aminophenoxy) biphenyl-3,3′-disulfonic acid and hydrophobic aromatic diamines showed the much lower methanol permeability and the lower proton conductivity than Nafion 112. The performance and the water and methanol crossover for direct methanol fuel cells (DMFCs) with the SPI membranes were investigated in comparison with Nafion membranes. The methanol and water fluxes increased significantly with increasing load current density for Nafion membranes but not for the SPI membranes, indicating that they were controlled by both the electro-osmotic drag and the molecular diffusion for the former but by only the molecular diffusion for the latter. These resulted in the much better DMFC performance for the SPIs than Nafion membranes especially at high methanol feed concentrations. The Faraday's efficiency and overall DMFC efficiency at 60 °C and 200 mA cm⁻² for SPI membrane with IEC of 1.51 meq g⁻¹ were 75% and 21%, respectively, at 5 wt.% methanol feed concentration, and 36% and 9.5%, respectively, at 20 wt.% methanol concentration. They were about two times and three times higher at 5 wt.% and 20 wt.% methanol concentrations, respectively, than those for Nafion 112. The short-term durability test for 300 h at 60 °C revealed no deterioration in the DMFC performance. The SPI membranes have high potential for DMFC applications at mediate temperatures (40–80 °C).     

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.     

Nafion-impregnated electrospun polyvinylidene fluoride composite membranes for direct methanol fuel cells

Composite membranes consisting of polyvinylidene fluoride (PVdF) and Nafion have been prepared by impregnating various amounts of Nafion (0.3–0.5 g) into the pores of electrospun PVdF (5 cm × 5 cm) and characterized by scanning electron microscopy, differential scanning calorimetry, X-ray diffraction, and proton conductivity measurements. The characterization data suggest that the unique three-dimensional network structure of the electrospun PVdF membrane with fully interconnected fibers is maintained in the composite membranes, offering adequate mechanical properties. Although the composite membranes exhibit lower proton conductivity than Nafion 115, the composite membrane with 0.4 g Nafion exhibits better performance than Nafion 115 in direct methanol fuel cell (DMFC) due to smaller thickness and suppressed methanol crossover from the anode to the cathode through the membrane. With the composite membranes, the cell performance increases on going from 0.3 to 0.4 g Nafion and then decreases on going to 0.5 g Nafion due to the changes in proton conductivity.     

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.     

Effect of operating conditions on the performance of a direct methanol fuel cell with PtRuMo/CNTs as anode catalyst

PtRu/CNTs and PtRuMo/CNTs catalysts have been synthesized by microwave-assisted polyol process and used as the anode catalysts for a direct methanol fuel cell (DMFC). The catalysts were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectrometry (XPS). The effect of different anode catalysts, membrane electrode assembly (MEA) activation, methanol concentration, methanol flow rate, oxygen flow rate and cell temperature on the DMFC performance has been investigated. The results show that the PtRu or PtRuMo particles with face-centered cubic structure are uniformly distributed on CNTs, and the addition of Mo to PtRu/CNTs makes the binding energies of each Pt species shift to lower values. PtRuMo/CNTs is a promising anode catalyst for DMFCs, and the appropriate operating conditions of the DMFC with PtRuMo/CNTs as the anode catalyst are MEA activation for 10 h, 2.0–2.5 M methanol at the flow rate of 1.0–2.0 mL/min, and oxygen at the flow rate of 100–150 mL/min. The DMFC performance increases significantly with an increase in cell temperature.     

Stable operation of air-blowing direct methanol fuel cells with high performance

A membrane electrode assembly (MEA) that is a combination of a catalyst-coated membrane (CCM) for the anode and a catalyst-coated substrate (CCS) for the cathode is studied under air-blower conditions for direct methanol fuel cells (DMFCs). Compared with MEAs prepared by only the CCS method, the performance of DMFC MEAs employing the combination method is significantly improved by 30% with less methanol crossover. This feature can be attributed to an enhanced electrode|membrane interface in the anode side and significantly higher catalyst efficiency. Furthermore, DMFC MEAs designed by the combination method retain high power density without any degradation, while the CCM-type cell shows a downward tendency in electrochemical performance under air-blower conditions. This may be due to MEAs with CCM have a much more difficult structure of catalytic active sites in the cathode to eliminate the water produced by electrochemical reaction. In addition, DMFCs produced via combination methods exhibit a lower water crossover flux than CCS alternatives, due to the comparatively dense structure of the CCM anode. Hence, DMFCs with a combination MEA structure demonstrate the feasibility of a small fuel cell system employing the low noise of a fan, instead of a noisy and large capacity air pump, for portable electronic devices.     

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.     

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.     

Effect of variation of hydrophobicity of anode diffusion media along the through-plane direction in direct methanol fuel cells

Reducing methanol crossover from the anode to cathode in direct methanol fuel cells (DMFCs) is critical for attaining high cell performance and fuel utilization, particularly when highly concentrated methanol fuel is fed into DMFCs. In this study, we present a novel design of anode diffusion media (DM) wherein spatial variation of hydrophobicity along the through-plane direction is realized by special polytetrafluoroethylene (PTFE) coating procedure. According to the capillary transport theory for porous media, the anode DM design can significantly affect both methanol and water transport processes in DMFCs. To examine its influence, three different membrane-electrode assemblies are fabricated and tested for various methanol feed concentrations. Polarization curves show that cell performance at high methanol feed concentration conditions is greatly improved with the anode DM design with increasing hydrophobicity toward the anode catalyst layer. In addition, we investigate the influence of the wettability of the anode microporous layer (MPL) on cell performance and show that for DMFC operation at high methanol feed concentration, the hydrophilic anode MPL fabricated with an ionomer binder is more beneficial than conventional hydrophobic MPLs fabricated with PTFE. This paper highlights that controlling wetting characteristics of the anode DM and MPL is of paramount importance for mitigating methanol crossover in DMFCs.