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.     

Performance of air-breathing direct methanol fuel cell with Au-coated aluminum current collectors

Current collectors of the direct methanol fuel cell (DMFC) are of significant importance for portable power sources, and greatly determine the weight energy density and cost of the cell. In this paper, the air-breathing aluminum (Al) current collectors have been developed for powering portable applications. The anode and cathode current collectors with the area of 4.5 cm² were fabricated on the Al substrates utilizing Computer Numerical Control (CNC) technology. To obtain strong anti-corrosion resistance, a 3-μm-Au layer was deposited on the current collectors using chemical plating. Compared with the graphite and stainless steel, the characterization of the Au-coated Al current collector was investigated to exhibit superior characteristics in electric conductivity, weight and electrochemical corrosion resistance. The current collector was applied to a DMFC and the cell performance was experimentally investigated under different operating conditions. The measured maximum power density of the DMFC could reach 19.8 mW cm⁻² at current density of 98 mA cm⁻² with 2 M methanol solutions. The results indicated that the Au-coated Al current collectors presented in this paper might be helpful for the development of portable power sources applied in future commercial applications.     

Development of an air-breathing direct methanol fuel cell with the cathode shutter current collectors

An air-breathing direct methanol fuel cell with a novel cathode shutter current collector is fabricated to develop the power sources for consumer electronic devices. Compared with the conventional circular cathode current collector, the shutter one improves the oxygen consumption and mass transport. The anode and cathode current collectors are made of stainless steel using thermal stamping die process. Moreover, an encapsulation method using the tailor-made clamps is designed to assemble the current collectors and MEA for distributing the stress of the edges and inside uniformly. It is observed that the maximum power density of the air-breathing DMFC operating with 1 M methanol solution achieves 19.7 mW/cm² at room temperature. Based on the individual DMFCs, the air-breathing stack consisting of 36 DMFC units is achieved and applied to power a notebook computer.     

Advanced air-breathing direct methanol fuel cells for portable applications

A novel MEA is fabricated to improve the performance of air-breathing direct methanol fuel cells. A diffusion barrier on the anode side is designed to control methanol transport to the anode catalyst layer and thus suppressing the methanol crossover. A catalyst coated membrane with a hydrophobic gas diffusion layer on the cathode side is employed to improve the oxygen mass transport. It is observed that the maximum power density of the advanced DMFC with 2 M methanol solution achieves 65 mW cm⁻² at 60 °C. The value is nearly two times more than that of a commercial MEA. At 40 °C, the power densities operating with 1 and 2 M methanol solutions are over 20 mW cm⁻² with a cell potential at 0.3 V.     

Structural diversity and orientation dependence of a liquid-fed passive air-breathing direct methanol fuel cell

This paper investigates the interesting effects of structural diversity and operating orientation on the performance of a liquid-fed passive air-breathing direct methanol fuel cell (PAB-DMFC). The results indicate that a higher thickness of the GEFC^®-10N membrane helps enhance the cell performance due to its ability in reducing methanol crossover (MCO). When the cell uses carbon cloth at the anode but carbon paper at the cathode as the diffusion media, it produces higher performances than other combinations. The work also confirms the merit of using a cathode diffusion layer since it improves water, methanol and heat management. As for the structural optimization of current collector, it is recommended to use the circular-hole-array pattern with a lower open ratio at the anode but the parallel-fence pattern with a higher open ratio at the cathode. It is further demonstrated that the vertical operation yields a higher cell performance at a lower methanol concentration while the horizontal operation performs better at a higher methanol concentration. Besides, the effects of opening pattern and working orientation on the CO₂ evolvement behaviors are analyzed by using visualized methods. Detailed mechanisms related to the resultant phenomena are comprehensively provided in this work.     

Operational characteristics of a passive air-breathing direct methanol fuel cell under various structural conditions

The operational characteristics of a small-scale passive air-breathing direct methanol fuel cell (PAB-DMFC) are comprehensively investigated under both steady-state and dynamic conditions. As the most important operating parameter, methanol concentration has significant effects on the cell performance. For different methanol concentrations (e.g., 0.5 and 8 M), the structural adaptations are particularly discussed. The results show that the structural factors are closely related to the influence degree of methanol concentration. In this study, the characteristics of the open circuit voltage (OCV) under various structural and methanol-concentration conditions are presented. Besides, the effects of other operating conditions such as running time, forced air convection and refueling action on the cell performance are also evaluated. In addition, a series of dynamic operations of the PAB-DMFC are conducted under different load cycles. Accordingly, the transient phenomena such as voltage undershoot and overshoot are explored. A fundamental principle for evaluating the operational characteristics of a PAB-DMFC is to simultaneously take into account the mass transfer requirements such as reactant delivery, product removal, methanol/water crossover control and so on.     

Performance of a direct methanol alkaline membrane fuel cell

A study of a direct methanol fuel cell (DMFC) operating with hydroxide ion conducting membranes is reported. Evaluation of the fuel cell was performed using membrane electrode assemblies incorporating carbon-supported platinum/ruthenium anode and platinum cathode catalysts and ADP alkaline membranes. Catalyst loadings used were 1 mg cm⁻² Pt for both anode and cathode. The effect of temperature, oxidant (air or oxygen) and methanol concentration on cell performance is reported. The cell achieved a power density of 16 mW cm⁻², at 60 °C using oxygen. The performance under near ambient conditions with air gave a peak power density of approximately 6 mW cm⁻².     

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.     

Electrochemical performance of an air-breathing direct methanol fuel cell using poly(vinyl alcohol)/hydroxyapatite composite polymer membrane

A novel composite polymer membrane based on poly(vinyl alcohol)/hydroxyapatite (PVA/HAP) was successfully prepared by a solution casting method. The characteristic properties of the PVA/HAP composite polymer membranes were examined by thermal gravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), micro-Raman spectroscopy and AC impedance method. An air-breathing DMFC, comprised of an air cathode electrode with MnO₂/BP2000 carbon inks on Ni-foam, an anode electrode with PtRu black on Ti-mesh, and the PVA/HAP composite polymer membrane, was assembled and studied. It was found that this alkaline DMFC showed an improved electrochemical performance at ambient temperature and pressure; the maximum peak power density of an air-breathing DMFC in 8 M KOH + 2 M CH₃OH solution is about 11.48 mW cm⁻². From the application point of view, these composite polymer membranes show a high potential for the DMFC applications.     

空气抽吸式甲醇燃料电池传热与传质特性

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

Performance characteristics of air-breathing anion-exchange membrane direct ethanol fuel cells

An air-breathing direct ethanol fuel cell (DEFC) with an anion-exchange membrane (AEM) and Pt-free electrodes is designed and investigated. Particular attention is paid to studying the performance characteristics of the air-breathing AEM DEFC. Experimental results reveal that this air-breathing AEM DEFC yields a peak power density as high as 38 mW cm⁻² at room temperature, which is comparable to the conventional Pt-based proton exchange membrane direct methanol fuel cells (PEM DMFCs). The overshoot/undershoot behaviors of both the cell voltage and cell temperature are avoided in the air-breathing AEM DEFC due to the use of ethanol-tolerant cathode catalyst. It is also found that the cathode water flooding behavior occurs in this air-breathing AEM DEFC, thus lowering the cell performance.     

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.     

An impedance study of an operating direct methanol fuel cell

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

Analysis of an active tubular liquid-feed direct methanol fuel cell

A two-dimensional, two-phase, non-isothermal model was developed for an active, tubular, liquid-feed direct methanol fuel cell (DMFC). The liquid-gas, two-phase mass transport in the porous anode and cathode was formulated based on the multi-fluid approach in the porous media. The two-phase mass transport in the anode and cathode channels was modeled using the drift-flux and the homogeneous mist-flow models, respectively. Water and methanol crossovers through the membrane were considered due to the effects of diffusion, electro-osmotic drag, and convection. The model enabled a numerical investigation of the effects of various operating parameters, such as current density, methanol flow rate, and oxygen flow rate, on the mass and heat transport characteristics in the tubular DMFC. It was shown that by choosing a proper tube radius and distance between the adjacent cells, a tubular DMFC stack can achieve a much higher energy density compared to its planar counterpart. The results also showed that a large anode flow rate is needed in order to avoid severe blockage of liquid methanol to the anode electrode due to the gas accumulation in the channel. Besides, lowering the flow rate of either the methanol solution or air can lead to a temperature increase along the flow channel. The methanol and water crossovers are nearly independent of the methanol flow rate and the air flow rate.     

Two-dimensional two-phase mass transport model for methanol and water crossover in air-breathing direct methanol fuel cells

A two-dimensional two-phase mass transport model has been developed to predict methanol and water crossover in a semi-passive direct methanol fuel cell with an air-breathing cathode. The mass transport in the catalyst layer and the discontinuity in liquid saturation at the interface between the diffusion layer and catalyst layer are particularly considered. The modeling results agree well with the experimental data of a home-assembled cell. Further studies on the typical two-phase flow and mass transport distributions including species, pressure and liquid saturation in the membrane electrode assembly are investigated. Finally, the methanol crossover flux, the net water transport coefficient, the water crossover flux, and the total water flux at the cathode as well as their contributors are predicted with the present model. The numerical results indicate that diffusion predominates the methanol crossover at low current densities, while electro-osmosis is the dominator at high current densities. The total water flux at the cathode is originated primarily from the water generated by the oxidation reaction of the permeated methanol at low current densities, while the water crossover flux is the main source of the total water flux at high current densities.     

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.     

Performance characteristics of a vapor feed passive miniature direct methanol fuel cell

In this paper, a new vapor feed fuel delivery system for a passive direct methanol fuel cell (DMFC) is developed and tested. Anode hydrophilic layers, electrical heating power and carbon dioxide release are examined to find their effects on the power density, efficiency and average temperatures of the cell. The hydrophilic layers act as a buffer layer between the vapor chamber and the anode gas diffusion layer (GDL). This layer allows water and methanol to mix, as well as distribute uniformly across the anode surface. Measurement of several parameters such as current, voltage, power, internal resistance, vapor chamber pressure, relative humidity and carbon dioxide concentration are taken. A maximum power density of 33 mW cm^?2 is achieved as well as 120 h of continuous operation at a constant current of 50 mA cm^?2 using the vapor feed system. The fuel utilization efficiency during the 120 h test is 34.8% and the energy efficiency is 8.2%.     

Performance of an alkaline-acid direct ethanol fuel cell

This paper reports on the performance of an alkaline-acid direct ethanol fuel cell (AA-DEFC) that is composed of an alkaline anode, a membrane and an acid cathode. The effects of membrane thickness and the concentrations of various species at both the anode and cathode on the cell performance are investigated. It has been demonstrated that the peak power density of this AA-DEFC that employs a 25-μm thick membrane is as high as 360 mW cm⁻² at 60 °C, which is about 6 times higher than the performance of conventional DEFCs reported in the literature.     

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.     

Performance characterization of passive direct methanol fuel cells

The performance of a fuel cell is usually characterized by a polarization curve (cell voltage versus current density) under stabilized operating conditions. However, for passive direct methanol fuel cells (DMFC) that have neither fuel pumps nor gas compressors, the voltage at a given current density varies with time because methanol concentration in the fuel reservoir keeps decreasing during the discharging process. The important question brought up by this transient discharging behavior is: under what conditions should the polarization data be collected such that the performance of the passive DMFC can be objectively characterized? In this work, we found that the performance of the passive DMFC became relatively stable as the cell operating temperature rose to a relatively stable value. This finding indicates that the performance of the passive DMFC can be characterized by collecting polarization data at the instance when the cell operating temperature under the open-circuit condition rises to a relatively stable value.