The Effect of Methanol Crossover on the Cathode Overpotential of DMFCs

The effects of methanol crossover on cathode overpotential of direct methanol fuel cells (DMFCs) were investigated by focusing on a mixed potential effect and surface poisoning of the catalyst. Experiments using different membranes and catalyst loadings were performed and compared with a semi‐quantitative model to discuss the main cause of the cathode overpotential. When the measured methanol crossover increased, cathode overpotential increased at particular threshold values, which were 150 mA cm^–2 at 0.3 mg cm^–2 of cathode platinum (Pt) loading and above 200 mA cm^–2 at 1.1 mg cm^–2. The modelling results also supported this tendency, and showed that Pt surface was poisoned to a great extent above the threshold methanol crossover where the cathode overpotential increased sharply, while the cathode overpotential remained low and was explained solely by the mixed potential below the threshold value. The threshold methanol crossover can be regarded as the acceptable value, below which the cathode overpotential from methanol crossover remains low, and was related with the Pt loading in the cathode. The reduction of methanol crossover through membranes below the acceptable values will contribute greatly to a decrease in the cathode overpotential and to the reduction of catalyst loadings.     

Development of a Direct Alcohol Alkaline Fuel Cell Stack

Direct alcohol alkaline fuel cells (DAAFC) are one of the potential fuel cell types in the category of low temperature fuel cells, which could become an energy source for portable electronic equipment in future. In the present study, a simple DAAFC stack has been developed and studied to evaluate the maximum performance for a given fuel (methanol or ethanol) and electrolyte (KOH) at various concentrations and temperatures. The open circuit voltage of the stack of four cells was nearly 4.0 V. A particular combination, 2 M fuel (methanol or ethanol) and 3 M KOH, results in maximum power density of the stack. The maximum power density obtained from the DAAFC stack (25 °C) was 50 mW cm^–2 at 20 mA cm^–2 for methanol and 17 mA cm^–2 for ethanol. The stack power density corroborated with that obtained from a single cell, indicating there was no further loss in the stack.     

Experimental and Numerical Study of Serpentine Flow Fields for Improving Direct Methanol Fuel Cell Performance

Methanol crossover is an important issue as it affects direct methanol fuel cell (DMFC) performance. But it may be controlled by selecting a proper flow field design. Experiments were carried out to investigate the effect of single, double and triple serpentine flow field configurations on a DMFC with a 25 cm² membrane electrode assembly (MEA) with a constant open ratio. A three dimensional model was also developed for the anode of the DMFC to predict methanol concentration and cell current density distributions. Experimental and model results show that at lower methanol concentrations (0.25–0.5M), single serpentine flow field (SSFF) provides high peak power density, while a double serpentine flow field (DSFF) gives high peak power density at a high methanol concentration (1–2M). Single and double serpentine flow fields exhibit the same peak power density (33 mW cm⁻²) at 1M. But the cell efficiency of double serpentine flow field is 12.5% which is 3.5% point greater than single serpentine flow field. This is attributed to reduced mixed potential. triple serpentine flow field (TSFF) shows the lowest peak power density and cell efficiency, which is attributed to high mass transfer resistance.     

Modeling Methanol Crossover by Diffusion and Electro-Osmosis in a Flowing Electrolyte Direct Methanol Fuel Cell

A CFD model is created to analyze methanol transport in a flowing electrolyte direct methanol fuel cell (FE-DMFC) by solving the 3D advection-diffusion equation, with consideration of electro-osmosis. The average methanol flux at the anode and cathode surfaces is simulated and compared to equivalent direct methanol fuel cells. Methanol crossover is defined as methanol flux at the cathode surface, and the results reveal that methanol crossover can be drastically reduced by the flowing electrolyte. The performance of the FE-DMFC at peak power current density is evaluated, and diffusion is shown to be the dominant contribution, although electro-osmosis increases with current density. The power consumption of the electrolyte pump is shown to be negligible compared to the cell power output. This indicates that thin electrolyte channels with high flow rates could further improve the efficiency.     

Development of a Self‐Adaptive Direct Methanol Fuel Cell Fed with 20 M Methanol

A passive and self‐adaptive direct methanol fuel cell (DMFC) directly fed with 20 M of methanol is developed for a high energy density of the cell. By using a polypropylene based pervaporation film, methanol is supplied into the DMFC's anode in vapor form. The mass transport of methanol from the cartridge to the anodic catalyst layer can be controlled by varying the open ratio of the anodic bipolar plate and by tuning the hydrophobicity of anodic diffusion layer. An effective back diffusion of water from the cathode to the anode through Nafion film is carried out by using an additive microporous layer in the cathode that consists of 50 wt.% Teflon and KB‐600 carbon. Accordingly, the water back diffusion not only ensures the water requirement for the methanol oxidation reaction but also reduces water accumulation in the cathode and then avoids serious water flooding, thus improving the adaptability of the passive DMFC. Based on the optimized DMFC structure, a passive DMFC fed with 20 M methanol exhibits a peak power density of 42 mW cm^–2 at 25 °C, and no obvious performance degradation after over 90 h continuous operation at a constant current density of 40 mA cm^–2.     

A Methanol Steam Micro-Reformer for Low Power Fuel Cell Applications

A micro-reformer was fabricated and its performance investigated using copper-zinc catalysts with differing compositions and loadings at various operating conditions. A catalyst with 3:1 copper-to-zinc ratio and 8 wt% loading produced enough hydrogen to power a 28W PEM fuel cell when using a third of the reformer's volume (8 cm³) and assuming 64% fuel cell efficiency. Methanol conversion was 65% while hydrogen content in the off-gas was 45% at a temperature of 275°C and residence time of 0.11s. Carbon monoxide levels were approximately 1.45%. Higher methanol conversions (80%) and hydrogen content in the off-gas (50%) were achieved by a second catalyst with 16 wt% at 290°C while utilizing the entire reformer volume. Hydrogen yield and selectivity were high (78 and 98% respectively). Extrapolating from present results, the maximum power output possible to be achieved by this device is 84 W.     

Performance of the Direct Methanol Carbonate Fuel Cell Using Anion Exchange Materials and Non‐Noble Metal Cathode Catalyst

A direct methanol fuel cell using a mixture of O₂ and CO₂ at the cathode was evaluated using anion exchange materials and cathode catalysts of Pt and a non‐Pt catalyst. The MEA based on non‐noble metal catalyst Acta 4020 showed superior performance than Pt/C based MEA in terms of open circuit potential and power density in carbonate environment. The fuel cell performance was improved by applying anion exchange ionomer in the catalyst layer. A maximum power density of 4.5 mW cm^–2 was achieved at 50 °C using 6.0 M methanol and 2.0 M K₂CO₃.     

The effect of two-layer cathode on the performance of the direct methanol fuel cell

To reduce the effect of methanol permeated from the anode, the structure of the cathode was modified from a single layer with Pt black catalyst to two-layer with PtRh black and Pt black catalysts, respectively. The current density of the direct methanol fuel cell (DMFC) using the two-layer cathode was improved to 228 mA/cm^-2 compared to that (180 mA/cm^-2) of the DMFC using the single layer cathode at 0.3 V and 303 K. From the cyclic voltammograms (CVs), it is indicated that the amount of adsorbates on the metal catalyst in the two-layer cathode is less than that of adsorbates in the single layer cathode after methanol test. In addition, the adsorbates were removed very rapidly by electrochemical oxidation from the two-layer cathode. It is suggested fromex situ X-ray absorption near edge structure analysis that the d-electron vacancy of Pt atom in the two-layer cathode is not changed by the methanol test. Thus, Pt is not covered with the adsorbates, which agrees well with the results of CV.     

Chitosan/titanate Nanotube Hybrid Membrane with Low Methanol Crossover for Direct Methanol Fuel Cells

Titanate nanotubes (TNTs) about 10 nm in diameter and 200–600 nm in length were hydrothermally synthesized, and then incorporated into a chitosan (CS) matrix to fabricate chitosan/titanate nanotube (CS/TNT) hybrid membranes for a direct methanol fuel cell (DMFC). These hybrid membranes were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray powder diffraction (XRD), thermogravimetry (TG), and positron annihilation lifetime spectroscopy (PALS). Moreover, their performances, including mechanical strength, water and methanol uptake, methanol permeability, and proton conductivity were determined. SEM results demonstrated that TNTs dispersed homogeneously in the hybrid membranes. Mechanical strength and TG measurements demonstrated that the mechanical and thermal stability of CS/TNT hybrid membranes were much higher than those of pure chitosan membranes. PALS analysis revealed that the fractional free volume (FFV) of CS/TNT hybrid membranes increased with the incorporation of TNTs and, thus, resulting in the reduction of methanol crossover. In all as‐prepared membranes, the hybrid membrane containing 15 wt % TNTs exhibited the highest mechanical strength of 85.0 MPa, low methanol permeability of 0.497 · 10^–6 cm²·s^–1, and proton conductivity of 0.0151 S·cm^–1, which had the potential for DMFC applications.     

A Visual Study of Bubble Formation in Microfluidic Fuel Cells

Two microfluidic fuel cells having microchannel widths of 1.0 mm (cell #1) and 0.5 mm (cell #2) with electrode spacing of 0.4 mm were tested at volumetric flow rates ranging from 0.1 to 1.0 ml min^–1. The concentration of hydrogen peroxide was tested at 0.1, 0.3, and 0.6 M. An additional microfluidic fuel cell (cell #3) having microchannel width of 0.5 mm and electrode spacing of 0.2 mm was also tested. Bubble formation under various tested conditions in different microchannels are presented. The open circuit voltage of the cells increased as reactant volumetric flow rate increased. Effect of electrode spacing on cell performance depends on the reactant concentration and volumetric flow rate. Also reported was the area‐specific internal resistance of the present cells and their fuel utilization corresponding to peak power density at a given flow rate with [H₂O₂] = 0.1 M. For cell #1, cell #2, and cell #3, respectively, the maximum power densities were 9, 40, and 16 mW cm^–2 at 1.0 ml min^–1 and 0.6 M, while the maximum power densities were 5, 11, and 15 mW cm^–2 at 1.0 ml min^–1 and 0.1 M.     

Long‐Term Stability Studies of Anode‐Supported Microtubular Solid Oxide Fuel Cells

A long‐term stability study of an anode‐supported NiO/YSZ‐YSZ‐LSM/YSZ microtubular cell was performed, under low fuel utilization conditions, using pure humidified hydrogen as fuel at the anode side and air at the cathode side. A first galvanometric test was performed at 766 °C and 200 mA cm^–2, measuring a power output at 0.5 V of ∼250 mW cm^–2. During the test, some electrical contact breakdowns at the anode current collector caused sudden current shutdowns and start‐up events. In spite of this, the cell performance remains unchanged. After a period of 325 h, the cell temperature and the current density was raised to 873°C and 500 mA cm^–2, and the cell power output at 0.5 V was ∼600 mW cm^–2. Several partial reoxidation events due to disturbance in fuel supply occurred, but no apparent degradation was observed. On the contrary, a small increase in the cell output power of about 4%/1,000 h after 654 h under current load was obtained. The excellent cell aging behavior is discussed in connection to cell configuration. Finally, the experiment concluded when the cell suffered irreversible damage due to an accidental interruption of fuel supply, causing a full reoxidation of the anode support and cracking of the thin YSZ electrolyte.     

Enhancement of the Passive Direct Methanol Fuel Cells Performance by Modification of the Cathode Microporous Layer Using Carbon Nanofibers

Mass transfer is a key parameter affecting the performance of the passive direct methanol fuel cells (DMFCs), which work under natural convection. In this study, effect of carbon nanofibers (CNFs) addition to the cathode microporous layer (MPL) on the performance of the passive DMFCs was investigated. The results indicated that CNFs content has a significant influence on both of the mass transport and the electrochemical surface area (ECSA). Interestingly, addition of the CNFs (20 wt.%) leads to increase the power density of the passive DMFC to 160% compared to pristine carbon black MPL. At low current density, the CNFs content has no influence on the performance, while at high current density the maximum performance can be obtained at 20 wt.% CNFs then the performance decreases with further increase in the CNFs content. Although the highest catalyst utilization is observed at 40 wt.% CNFs, a maximum power density of 36 mW cm^–2 can be obtained at 20 wt.% CNFs and this is related to the significant effect of the mass transfer resistance under the passive operation conditions. Overall, addition of CNFs to the MPL can be considered an effective strategy to modify the passive DMFCs performance.     

A direct methanol fuel cell using acid-doped polybenzimidazole as polymer electrolyte

A direct methanol/oxygen solid polymer electrolyte fuel cell was demonstrated. This fuel cell employed a 4 mg cm^–2 Pt-Ru alloy electrode as an anode, a 4 mg cm^–2 Pt black electrode as a cathode and an acid-doped polybenzimidazole membrane as the solid polymer electrolyte. The fuel cell is designed to operate at elevated temperature (200°C) to enhance the reaction kinetics and depress the electrode poisoning, and reduce the methanol crossover. This fuel cell demonstrated a maximum power density about 0.1 W cm^–2 in the current density range of 275–500 mA cm^–2 at 200°C with atmospheric pressure feed of methanol/water mixture and oxygen. Generally, increasing operating temperature and water/methanol mole ratio improves cell performance mainly due to the decrease of the methanol crossover. Using air instead of the pure oxygen results in approximately 120 mV voltage loss within the current density range of 200–400 mA cm^–2 .     

Empirical Model Equations for the Direct Methanol Fuel Cell DMFCs

Empirical model equations, proposed for polymer electrolyte fuel cells, are used to predict the cell voltage vs. current density response of a liquid feed direct methanol fuel cell. The model equations are validated against experimental data for a small-scale fuel cell over a wide range of methanol concentration and temperatures. A new empirical equation is presented which is able to predict the voltage response of liquid feed direct methanol fuel cells over a wide range of operating conditions and even in the case of very low current densities caused by, for example, the use of dilute methanol solutions or low cell temperatures.     

Synthesis of Dendritic Nano‐Sized Nickel for use as Anode Material in an Alkaline Membrane Fuel Cell

Dendritic nano‐sized nickel nanoparticles were synthesised using a hydrazine reduction method in ethylene glycol from a nickel chloride precursor. The resulting particles were characterised by X‐ray diffraction (XRD), scanning electron microscopy (SEM) and Transmission Electron Microscopy (TEM). Dendritic nickel has a network structure which is ideal to be used as electrode for electrochemical devices such as fuel cells. The prepared dendritic nickel nanoparticles were used as anodes for an alkaline membrane fuel cell using poly(vinyl)alcohol (PVA)/tetraethyl ammonium chloride (TEAC) alkaline blend electrolyte membrane with a PVA/TEAC ratio of 1:5. A current density of 11.5 mA cm^–2 has been achieved when methanol was used as the fuel.     

Effect of Porosity in Catalyst Layers on Direct Methanol Fuel Cell Performances

Effects of porosity of catalyst layers (CLs) on direct methanol fuel cell (DMFC) performances are investigated using silicon dioxide (SiO₂) particles as a pore former. The pore size and volume of CLs are controlled by changing the size and content of SiO₂. As the size of pore formed by removal of SiO₂ increases, DMFC performances are enhanced. The augmentation in performances can be explained by facilitation of fuel transport to catalyst particles, increase of utilization efficiency of catalysts, diminishment in methanol crossover, reduction in activation loss and facilitation of water discharging out of CLs of cathode due to the controlled porosity in CLs. The enhanced fuel transport, accessibility of fuels to Pt catalyst surface, is proved by the active areas of Pt catalyst. In addition to the active area of Pt catalyst, porous CLs exhibit a decline in methanol crossover, leading to increase of open circuit voltage (OCV). The porous CLs also show improvements in activation loss due to high porosity, causing enhancement in DMFC performances. In aspect of pore volume contribution to cathode performance, the SiO₂ content is optimized. Based on the DMFC performances, it can be suggested that the optimum conditions of SiO₂ are 500 nm in size and 20 wt.% in content. The porosity effect on both electrodes appears as follows: the pores in cathode are more effective on DMFC performances (55.5%) than those of anodes (44.5%) based on the maximum power of DMFC, indicating that the pores in CLs facilitate removal of water from electrodes.     

Combinatorial Search for Quaternary Methanol Tolerant Oxygen Electro‐Reduction Catalyst

A combinatorial library containing 645 different compositions was synthesised and characterised for methanol tolerant oxygen electro‐reduction reaction (ORR) catalytic performance. The library was composed of compositions involving between 1 and 4 metals among Pt, Ru, Fe, Mo and Se. In an optical screening test, Pt(50)Ru(10)Fe(20)Se(10) composition exhibited the highest ORR activity in the presence of methanol. This composition was further investigated by synthesis and characterisation of a powder version catalyst [Pt(50)Ru(10)Fe(20)Se(10)/C]. At 0.85 V [vs. reversible hydrogen electrode (RHE)] in the absence of methanol, the Pt/C catalyst exhibited higher ORR current (0.0990 mA) than the Pt(50)Ru(10)Fe(20)Se(10)/C catalyst (0.0902 mA). But much higher specific activity (12.7 μA cm_pt^–2) was observed in the Pt(50)Ru(10)Fe(20)Se(10)/C catalyst than for the Pt/C catalyst 6.51 μA cm_pt^–2). In the presence of methanol, the ORR current decreased by 0.0343 and 0.247 mA for the Pt(50)Ru(10)Fe(20)Se(10)/C and Pt/C catalysts, respectively, which proved the excellent methanol tolerance of the Pt(50)Ru(10)Fe(20)Se(10)/C catalyst.     

Operation of the Alkaline Direct Formate Fuel Cell in the Absence of Added Hydroxide

The direct formate fuel cell (DFFC) has recently been demonstrated as a viable alkaline direct liquid fuel cell (DLFC) that does not require addition of hydroxide to the fuel stream for operation. In this work, we report that the DFFC can produce significant power at low temperatures without added hydroxide, especially when compared with other alkaline DLFCs powered by alcohols. Using oxygen at the cathode, the DFFC powered by 1 M HCOOK achieves a maximum power density of 106 mW cm^–2 at 50 °C and 64 mW cm^–2 at 23 °C. Using air at the cathode, the same DFFC achieves a maximum power density of 76 mW cm^–2 at 50 °C and 27 mW cm^–2 at 23 °C. These power densities were achieved without addition of hydroxide to the fuel stream. Constant current operation demonstrates that the maximum power density can be maintained at least for several hours of operation. Finally, we use electrochemical analysis to demonstrate that the formate oxidation reaction is not dependent on pH between 9 and 14, which permits the use of formate fuel without added hydroxide in the DFFC. An alkaline DLFC that does not require added hydroxide is promising for safe and practical operation.     

Arsenic removal from drinking water by electrocoagulation using iron electrodes

Arsenic removal from drinking water was investigated using electrocoagulation (EC) followed by filtration. A sand filter was used to remove flocs generated in the EC process. Experiments were performed in a batch electrochemical reactor using iron electrodes with monopolar parallel electrode connection mode to assess their efficiency. The effects of several operating parameters on arsenic removal such as current density (1.5–9.0 mA cm^?2), initial arsenic concentration (50–500 μg L^?1), operating time (0–15 min), electrode surface area (266–665 cm²), and sodium chloride concentrations (0.01 and 0.02M) were examined. The EC process was able to decrease the residual arsenic concentration to less than 10 μg L^?1. Optimum operating conditions were determined as an operating time of 5 min and current density of 4.5 mA cm^?2 at pH of 7. The optimum electrode surface area for arsenic removal was found to be 266 cm² taking into consideration cost effectiveness. The residual iron concentration increased with increasing residence time, and maximum residual iron value was measured as 287 μg L^?1 for electrode surface area of 266 cm². The addition of sodium chloride had no significant effect on residual arsenic concentration, but an increase in current density was observed.     

Ionically Cross‐Linked Proton Conducting Membranes for Fuel Cells

For improving stability without sacrificing ionic conductivity, ionically cross‐linked proton conducting membranes are fabricated from Na⁺‐form sulfonated poly(phthalazinone ether sulfone kentone) (SPPESK) and H⁺‐formed sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (SPPO). Ionically acid‐base cross‐linking between sulfonic acid groups in SPPO and phthalazone groups in SPPESK impart the composite membranes the good miscibility and electrochemical performance. In particular, the composite membranes possess proton conductivity of 60–110 mS cm⁻¹ at 30 °C. By controlling the protonation degree of SPPO within 40–100 %, the composite membranes with favorable cross‐linking degree are qualified for application in fuel cells. The maximum power density of the composite membrane reaches approximately 1100 mW cm⁻² at the current density of 2800 mA cm⁻² at 70 °C.