Fabrication of MEA with hydrocarbon based membranes using low temperature decal method for DMFC

The membrane electrode assembly (MEA) with hydrocarbon (HC) based membranes made by a low temperature decal method has been investigated for the direct methanol fuel cells (DMFCs). The conventional low temperature decal (LTD) transfer method (comprised of three layers; viz., carbon, Nafion bonded electrodes and outer ionomer layers over the decal Teflon substrates) meant for the MEAs made of Nafion type membranes is suitably modified to use with hydrocarbon (HC) based membranes. The modification of conventional LTD method is effected by means of modulating the three-layered structure and optimizing other parameters to facilitate complete transfer of catalyst layers onto the HC membranes. The MEAs prepared by the modified LTD method have yielded 21 % higher DMFC performance compared to that of the MEAs produced by conventional LTD method. The structure and electrochemical properties of the MEAs have been analyzed by the field-emission scanning electron microscopy (FE-SEM) and the electrochemical impedance spectroscopy (EIS).     

The performance and mechanism of multi-step activation of MEA for DMFC

Membrane electrode assembly (MEA) after hot-pressing could not achieve its best performance before activated properly because the passages for protons, electrons, reactants and products in the MEA are not constituted completely. In this research, effective multi-step activation for MEA was proposed and the mechanism was discussed. The process includes three steps: methanol activation at room temperature, forced activation at intermediate temperature and proton activation at intermediate temperature. The performance of the MEA was correspondingly improved and reached respectively 54 mW cm⁻², 61 mW cm⁻², 78 mW cm⁻², after each step of the activation. Apparently the performance was greatly enhanced by multi-step activation. The activation process of MEA is not only a process of the humidification of the proton exchange membrane but also a complex process for the establishment of the channels for electrons, ions, gases and liquids. Furthermore the conduction of electrons, ions and the transportation of the reactants and products are enhanced while the micro-structure of the MEA is kept stable.     

Long-term durability test for direct methanol fuel cell made of hydrocarbon membrane

A long-term durability test has been conducted for a direct methanol fuel cell (DMFC) using the commercial hydrocarbon membrane and Nafion ionomer bonded electrodes for 500 h. Membrane electrode assembly (MEA) made by a decal method has experienced a performance degradation about 34% after 500 h operation. Cross-sectional analysis of the MEA shows that the poor interfacial contact between the catalyst layers and membrane in the MEA has further deteriorated after the durability test. Therefore, the internal resistance of a cell measured by electrochemical impedance spectroscopy (EIS) has considerably increased. The delamination at the interfaces is mainly attributed to incompatibility between polymeric materials used in the MEA. Furthermore, X-ray diffraction (XRD) analysis reveals that the catalyst particles have grown; thereby decreasing the electrochemical surface area. Electron probe micro analysis (EPMA) shows a small amount of Ru crossover from anode to cathode; and its effect on the performance degradation has been analyzed.     

High performance membrane electrode assemblies by optimization of coating process and catalyst layer structure in direct methanol fuel cells

High performance membrane electrode assemblies (MEAs) for direct methanol fuel cells (DMFCs) are developed by changing the coating process, optimizing the structure of the catalyst layer, adding a pore forming agent to the cathode catalyst layer, and adjusting the hot-pressing conditions, such as pressure and temperature. The effects of these MEA fabrication methods on the DMFC performance are examined using a range of physicochemical and electrochemical analysis tools, such as FE-SEM, electrochemical impedance spectroscopy (EIS), polarization curves, and differential scanning calorimetry (DSC) of the membrane. EIS and polarization curve analysis show that an increase in the thickness and porosity of the cathode catalyst layer plays a key role in improving the cell performance with reduced cathode reaction resistance, whereas the MEA preparation methods have no significant effects on the anode impedance. In addition, the addition of magnesium sulfate as a pore former reduces the cathode reaction transfer resistance by approximately 30 wt%, resulting in improved cell performance.     

Characterization of electrode structures and the related performance of direct methanol fuel cells

The performance of membrane electrode assemblies (MEAs) in fuel cells is substantially affected by the structures of the electrodes. An increase of about 25% in power performance was achieved merely by controlling the pressure of hot press in the MEA fabrication process for a given Pt loading, instead of by employing pore formers and heat treatment-a widely accepted method-to modify the structures of the electrode. The microstructures of the different hot-pressed electrodes were examined by transmission electron microscopy, scanning electron microscopy, and small angle X-ray scattering to assess the effect of the pressure on the structures of the electrodes. Based on experimental observations, the improved performance of the MEA is attributed to the porosity of the cathode electrode, in which a network of macrofissures and sub-microfissures allows air to penetrate the electrode. Emphasis is also placed on the relationship between the total porosity of the electrodes and the MEA performance. Results of this study demonstrate that the specific power density nearly doubles when the total porosity increased from 57% to 76%. Also, the MEAs mounted in an air-breathing DMFC small pack were fabricated in-house to supply power for a mobile phone.     

Performance test and degradation analysis of direct methanol fuel cell membrane electrode assembly during freeze/thaw cycles

Performance and degradation of direct methanol fuel cell (DMFC) membrane electrode assembly (MEA) are analyzed after repeated freeze/thaw cycles. Three different MEAs stored at −20 °C for 8 h with the anode side full of methanol solution are selected to test the effects of low temperatures on performance. After the cell heated to 60 °C within 30 min, they are inspected to determine the degradation mechanism. The resistance R obtained by the polarization curve is essential for identifying the main component affecting cell performance. The electrochemical impedance spectroscopy (EIS) technique is used to characterize the DMFC after freeze/thaw cycles. Thus, deterioration is assessed by measuring the high-frequency resistance (HFR) and the charge-transfer resistance (CTR). The electrochemical surface area (ECA) is employed to investigate not only the actual chemical degradation but also membrane status since sudden loss of ECA on the cathode side can result from a broken membrane. Moreover, a strategy is designed to simulate actual conditions that may prevent the membrane from being broken. A DMFC stack without any heating or heat-insulation devices shall avoid to be stored at subzero temperatures since the membrane will be useless due to frozen of methanol solution.     

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

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

Effects of hot pressing conditions on the performances of MEAs for direct methanol fuel cells

The effects of hot pressing conditions (hot pressing temperature, pressure and time) on the performances of membrane electrode assemblies for direct methanol fuel cells were investigated. The performances of membrane electrode assemblies (MEAs) were characterized by the polarization curves and electrochemical impedance spectra (EIS). The surface morphologies of the electrodes were observed by scanning electron microscopy (SEM). The compression ratios of electrodes were determined by testing the thicknesses of the anodes and the cathodes before and after the hot pressing process. The MEA which was hot pressed at 135 °C under 80 kg cm⁻² for 90 s, showed the highest power density of 46.0 mW cm⁻² at 80 °C and ambient pressure. As the hot pressing temperature, pressure and time increased, the compression ratios of the anodes and cathodes increased, and the activating time required for MEA to reach optimum performance increased, too. The cell resistances of the MEAs hot pressed at higher hot pressing temperature (135 °C) and pressure (120 kg cm⁻²), or for longer time (90 s), decreased because of the good contact between the membrane and electrodes. The MEAs that were hot pressed under higher temperature (135 °C) and higher pressure (120 kg cm⁻²) benefited for long-time cell operating.     

On the electrochemical impedance spectroscopy of direct methanol fuel cell

The direct methanol fuel cell (DMFC) was operated under a variety of current densities to monitor the electrochemical impedance spectroscopy (EIS) for understanding its reaction mechanism. Based on the EIS analysis, the impedance of the cell reaction is divided into three components, two of them are current dependent and the remainder is current independent. Through detailed exploration of the impedance components, the high-frequency impedance was attributed to interfacial behavior, the medium-frequency impedance to electrochemical reactions, and the low-frequency impedance to the adsorption/relaxation of CO. Based on EIS analysis, a qualitative model is proposed to delineate the reaction mechanisms of DMFC, which is confirmed quantitatively by one set of equivalent circuit elements. The experimental data are satisfactorily consistent with the results simulated from the proposed model.     

Development of a tubular microbial fuel cell (MFC) employing a membrane electrode assembly cathode

Tubular microbial fuel cells (MFC) with air cathode might be amenable to scale-up but with increasing volume a mechanically robust, cost-effective cathode structure is required. Membrane electrode assemblies (MEA) are investigated in a tubular MFC using cost-effective cation (CEM) or anion (AEM) exchange membrane. The MEA fabrication mechanically combines a cathode electrode with the membrane between a perforated cylindrical polypropylene shell and tube. Hydrogel application between membrane and cathode increases cathode potential by ∼100 mV over a 0–5.5 mA range in a CEM-MEA. Consequently, 6.1 W m⁻³ based on reactor liquid volume (200 cm³) are generated compared with 5 W m⁻³ without hydrogel. Cathode potential is also improved in AEM-MEA using hydrogel. Electrochemical Impedance Spectroscopy (EIS) to compare MEA's performance suggests reduced impedance and enhanced membrane–cathode contact area when using hydrogel. The maximum coulombic efficiency observed with CEM-MEA is 71% and 63% with AEM-MEA. Water loss through the membrane varies with external load resistance, indicating that total charge transfer in the MFC is related to electro-osmotic drag of water through the membrane. The MEA developed here has been shown to be mechanically robust, operating for more than six month at this scale without problem.     

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.     

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

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

Effects of porous and dense electrode structures of membrane electrode assembly on durability of direct methanol fuel cells

This study addresses how durability of direct methanol fuel cells (DMFCs) is involved with the electrode structures of membrane electrode assembly (MEA) with different porosity and microstructures. The different electrode structures of the MEAs (porous (MEA-1) and dense (MEA-2) electrode structure) bring about the difference in the reaction kinetics associated with the electrochemical active surface area (ECSA) and in mass transport on the electrodes. The dense electrode structures of the MEA-2 cause the continual non-uniformity of the mass transport-related phenomena at the cathode, and thereby the catalysts of the MEA-2 experience much severer particle growth and agglomeration to decrease ECSA and activity of the catalysts. During the long-term operation, the decay rate of the MEA-2 was faster by more than three times compared to the MEA-1 with the relatively porous electrode structures. These results show that an electrode structure of a MEA is an important factor to govern durability of DMFCs.     

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.     

Improved mass transfer using a pore former in cathode catalyst layer in the direct methanol fuel cell

The cathode catalyst layer in direct methanol fuel cells (DMFCs) was prepared using polystyrene beads as a pore former. Field emission scanning electron microscopy showed that the catalyst layer with the pore former contained pores with a uniform shape and size. Mercury intrusion porosimetry showed that the pore former increased the volume of secondary pores in the catalyst layer. The electrochemical properties of the membrane electrode assembly (MEA) were evaluated by current–voltage polarization measurements, electrochemical impedance spectroscopy and cyclic voltammetry. These results suggest that the catalyst layer with the pore former reduces the mass transfer resistance and improves the cell performance by approximately 50% through modification of its morphology.     

Enhanced performance of a passive direct methanol fuel cell with decreased Nafion aggregate size within the anode catalytic layer

The decrease in Nafion ionomer size within the anode catalytic layer for a passive direct methanol fuel cell (DMFC) results in a significant enhancement in fuel cell’s performance. Dynamic light scattering measurement demonstrates that the agglomerate size of Nafion ionomer in the solution decreases and the aggregate particle size distribution becomes narrow until a monodispersed Nafion ionomer was obtained with an increase in heat treatment temperature. The improved performance of the passive DMFC with smaller Nafion ionomer agglomerates within the anode catalytic layer can be ascribed to a decrease in charge-transfer resistance of anodic reaction obtained by electrochemical impedance analysis and to an improvement in catalyst utilization verified by cyclic voltammetric measurement. Furthermore, the small congeries formed between catalyst nanoparticles and Nafion ionomers could lead to a decrease in Nafion loading within the catalytic layer. This study confirms that the decrease in Nafion aggregation within the catalytic ink is beneficial to an improvement in both catalyst and Nafion ionomer utilization, thus enhancing fuel cell’s performance.     

A theoretical model of the membrane electrode assembly of liquid feed direct methanol fuel cell with consideration of water and methanol crossover

An algebraic model of the membrane electrode assembly of the direct methanol fuel cell is developed, which considers the simultaneous liquid water and methanol crossover effects, and the associated electrochemical reactions. The respective anodic and cathodic polarization curves can be predicted using this model. Methanol concentration profile and flux are correlated explicitly with the operating conditions and water transport rate. The cathode mixed potential effect induced by the methanol crossover is included and the subsequent cell voltage loss is identified. Water crossover is influenced by the capillary pressure equilibrium and hydrophobic property within the cathode gas diffusion layer. The model can be used to evaluate the cell performance at various working parameters such as membrane thickness, methanol feed concentration, and hydrophobicity of the cathode gas diffuser.     

A self-pumping and self-breathing micro direct methanol fuel cell with polymer bipolar plates

A passive micro direct methanol fuel cell (DMFC) for reducing volume and parasitic power is designed and fabricated using several integrated technologies. New bipolar plates with tapered channels at the anode and a pillar array at the cathode are first applied to a passive micro-DMFC. The substrate of the bipolar plates made of acrylonitrile butadiene styrene (ABS) is hot embossed with two molds, fabricated by UV-LIGA and micro machining. To make the bipolar plates conductive and hydrophilic, a nickel layer is electroplated on the ABS plates, and three PDDA/PSS bi-layers are self-assembled onto the nickel layer. The bipolar plates are produced using hot embossing, a low cost, highly accurate batch process. A single cell is assembled to verify the self-pumping function, and it can generate a peak power density of 7.4 mW cm⁻² with a 3 M methanol solution. The fuel cell is verified to work in three different orientations. When the fuel cell is placed horizontally, the self-pumping rate is about 0.1-0.15 mL h⁻¹. And the fuel cell can work through self-pumping for 5 h under this condition.     

The possible failure mode and effect analysis of membrane electrode assemblies and their potential solutions in direct methanol fuel cell systems for portable applications

One of the major challenges in direct methanol fuel cells (DMFCs) is to design reliable and stable FC systems that satisfy the very high dynamic demand in various environmental conditions for portable devices. This paper provides an overview of several failure modes and effect analyses (FMEAs) which can have significant consequences on the durability and stability of DMFCs, including high and sub-zero temperature storage, dry and high humidification atmospheres, and fuel/oxidation starvation by breakdown of fuel/air supply components. Firstly, some characterization methods are discussed to investigate changes of membrane electrode assemblies (MEAs) in terms of their physiochemical and electrochemical properties after testing in various simulated failure modes. Secondly, possible mitigating solutions to minimize the hazards associated with them are suggested through a fundamental understanding and scientific approach. The relationship between the causes and symptoms in DMFC systems is determined by examining a variety of failure sources.     

Fabrication and evaluation of membrane electrode assemblies by low-temperature decal methods for direct methanol fuel cells

In this study, a low-temperature decal transfer method is used to fabricate membrane electrode assemblies (MEAs) and the MEAs are tested for application in a direct methanol fuel cell (DMFC). The low-temperature decal transfer uses a carbon-layered decal substrate with a structure of ionomer/catalyst/carbon/substrate to facilitate the transfer of catalyst layers from the decal substrates to the membranes at a temperature as low as 140 °C, and also to prevent the formation of ionomer skin layer that is known to be formed on the surface of the transferred catalyst layer. The DMFC performance of the MEA (with carbon layer) fabricated by the low-temperature decal transfer method is higher than those of MEAs fabricated by the same method without a carbon layer, a conventional high-temperature decal method, and a direct spray-coating method. The improved DMFC performance of the MEA fabricated with carbon layer by the low-temperature decal transfer method can be attributed to the absence of an ionomer skin on the catalyst layer, which can streamline the diffusion of reactants. Furthermore, the intrinsic properties of the MEA fabricated by the low-temperature decal transfer method are elucidated by field-emission scanning electron microscopy (FESEM), electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) techniques, and cathode CO₂ analysis.