A study on the dissymmetrical microporous layer structure of a direct methanol fuel cell

The effect of carbon type, carbon loading and microporous layer structure in the microporous layer on the performance of a direct methanol fuel cell (DMFC) at low temperature was investigated using electrochemical polarization techniques, electrochemical impedance spectroscopy, scanning electron microscope and other methods. Vulcan XC-72 carbon was found to be most suitable as a microporous layer for low temperature DMFC. Maximum fuel cell performance was obtained utilizing a microporous layer with carbon loading of 1.0 mg cm⁻² when air was used as an oxidant. A membrane electrode assembly with 1.0 mg cm⁻² Vulcan XC-72 carbon with 20 wt.% Teflon in the cathode and no microporous layer in the anode showed a maximum power density of 36.7 mW cm⁻² at 35 °C under atmospheric pressure. The AC impedance study proved that a cell with a dissymmetrical microporous layer structure had lower internal resistance and mass transfer resistance, thus obtaining better performance.     

Investigation of carbon-supported Pt and PtCo catalysts for oxygen reduction in direct methanol fuel cells

Carbon-supported Pt and Pt₃Co catalysts with a mean crystallite size of 2.5 nm were prepared by a colloidal procedure followed by a carbothermal reduction. The catalysts with same particle size were investigated for the oxygen reduction in a direct methanol fuel cell (DMFC) to ascertain the effect of composition. The electrochemical investigations were carried out in a temperature range from 40 to 80 °C and the methanol concentration feed was varied in the range 1-10 mol dm⁻³ to evaluate the cathode performance in the presence of different conditions of methanol crossover. Despite the good performance of the Pt₃Co catalyst for the oxygen reduction, it appeared less performing than the Pt catalyst of the same particle size for the cathodic process in the presence of significant methanol crossover. Cyclic voltammetry analysis indicated that the Pt₃Co catalyst has a lower overpotential for methanol oxidation than the Pt catalyst, and thus a lower methanol tolerance. Electrochemical impedance spectroscopy (EIS) analysis showed that the charge transfer resistance for the oxygen reduction reaction dominated the overall DMFC response in the presence of high methanol concentrations fed to the anode. This effect was more significant for the Pt₃Co/KB catalyst, confirming the lower methanol tolerance of this catalyst compared to Pt/KB. Such properties were interpreted as the result of the enhanced metallic character of Pt in the Pt₃Co catalyst due to an intra-alloy electron transfer from Co to Pt, and to the adsorption of oxygen species on the more electropositive element (Co) that promotes methanol oxidation according to the bifunctional theory.     

Development and characterization of a silicon-based micro direct methanol fuel cell

A silicon-based micro direct methanol fuel cell (μDMFC) for portable applications has been developed and its electrochemical characterization carried out in this study. Anode and cathode flowfields with channel and rib width of 750 μm and channel depth of 400 μm were fabricated on Si wafers using the microelectromechanical system (MEMS) technology. A membrane-electrode assembly (MEA) was specially fabricated to mitigate methanol crossover. This MEA features a modified anode backing structure in which a compact microporous layer is added to create an additional barrier to methanol transport thereby reducing the rate of methanol crossing over the polymer membrane. The cell with the active area of 1.625 cm² was assembled by sandwiching the MEA between two micro-fabricated Si wafers. Extensive cell polarization testing demonstrated a maximum power density of 50 mW/cm² using 2 M methanol feed at 60 °C. When the cell was operated at room temperature, the maximum power density was shown to be about 16 mW/cm² with both 2 and 4 M methanol feed. It was further found that the present μDMFC still produced reasonable performance under 8 M methanol solution at room temperature.     

Influence of copper oxide modification of a platinum cathode on the activity of direct methanol fuel cell

To determine whether a copper oxide modified Pt cathode (PtCuO_m) improves a performance of direct methanol fuel cells (DMFC), we performed structural and morphological analysis of the cathode and measured current-potential profile and impedance spectroscopy. Comparing with an unmodified Pt cathode, we found that PtCuO_m prepared by rf sputtering techniques induced higher oxygen reduction reaction rate and suppressed electrocatalytic oxidation of methanol, which is the main reason of the mixed potential occurred at a cathode. Therefore, PtCuO_m increased the power performance of DMFC applying both oxygen and air and electrochemical impedance spectra clearly supported the difference of the performance between unmodified and modified Pt electrodes. These results may play a role in better long-term stability of DMFC systems.     

Nafion-TiO2 composite DMFC membranes: physico-chemical properties of the filler versus electrochemical performance

TiO₂ nanometric powders were prepared via a sol-gel procedure and calcined at various temperatures to obtain different surface and bulk properties. The calcined powders were used as fillers in composite Nafion membranes for application in high temperature direct methanol fuel cells (DMFCs). The powder physico-chemical properties were investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and pH measurements. The observed characteristics were correlated to the DMFC electrochemical behaviour. Analysis of the high temperature conductivity and DMFC performance reveals a significant influence of the surface characteristics of the ceramic oxide, such as oxygen functional groups and surface area, on the membrane electrochemical behaviour. A maximum DMFC power density of 350 mW cm⁻² was achieved under oxygen feed at 145 °C in a pressurized DMFC (2.5 bar, anode and cathode) equipped with TiO₂ nano-particles based composite membranes.     

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.     

A method for determining anode and cathode impedances of a direct methanol fuel cell running on a load

A new method for measuring separately anode and cathode impedances (Z_A and Z_C) of an electrochemical generator running on constant load is proposed. In these conditions, the measurement of Z_A and Z_C is not as simple as under galvanostatic conditions. Measurements are carried out first on a dummy cell and next on a commercial direct methanol fuel cell (DMFC) under galvanostatic conditions and using the new proposed method. The comparison of the results validate our method, showing that it is a powerful method for fuel cell electrochemical impedance spectroscopy (EIS) characterization under natural running conditions.     

Performance degradation study of a direct methanol fuel cell by electrochemical impedance spectroscopy

A stability test of a direct methanol fuel cell (DMFC) was carried out by keeping at a constant current density of 150 mA cm⁻² for 435 h. After the stability test, maximum power density decreased from 68 mW cm⁻² of the fresh membrane-electrode-assembly (MEA) to 34 mW cm⁻² (50%). Quantitative analysis on the performance decay was carried out by electrochemical impedance spectroscopy (EIS). EIS measurement of the anode electrode showed that the increase in the anode reaction resistance was 0.003 Ω cm². From the EIS measurement results of the single cell, it was found that the increase in the total reaction resistance and IR resistance were 0.02 and 0.05 Ω cm², respectively. Summarizing the EIS measurement results, contribution of each component on the performance degradation was determined as follows: IR resistance (71%) > cathode reaction resistance (24%) > anode reaction resistance (5%). Transmission electron microscopy (TEM) results showed that the average particle size of the Pt catalysts increased by 30% after the stability test, while that of the PtRu catalysts increased by 10%.     

Pore‐forming technology and performance of MEA for direct methanol fuel cells

BACKGROUND: The commercialization of DMFCs is seriously restricted by its relatively low power density. Lots of work has been concentrated on catalysts with high activity, the optimization of flow path design, development of new kinds of proton exchange membrane and modification of Nafion membrane. Meanwhile, very few reports have involved the structure optimization of the membrane electrode assembly (MEA). To improve the performance of direct methanol fuel cells (DMFCs), the catalyst layer (CL) structures of anode and cathode were optimized by utilizing ammonium carbonate as pore forming agent. RESULTS: The polarization curves showed that in catalyst slurry the optimal content of ammonium carbonate was 50 wt%, and the DMFC performance was enhanced from 75.65 mW cm^?2 to 167.42 mW cm^?2 at 55 °C and 0.2 MPa O₂. Electrochemical impedance spectroscopy and electrochemical active surface area (EASA) testing revealed that the improved performance of optimized MEAs could be mainly attributed to the increasing EASA and the enhanced mass transfer rate of CLs. But poor methanol crossover limited the performance enhancement of MEAs with porous anodes. CONCLUSION: With regard to improving cell performance, this pore‐forming technology is better applied to the cathode catalyst layer to improve its structure rather than the anode catalyst layer. © 2012 Society of Chemical Industry     

Physical and electrochemical characterization of catalysts for oxygen reduction in fuel cells

The cathode catalysts in low temperature fuel cells are associated with major cell efficiency losses, because of kinetic limitations of the oxygen reduction reaction. Additionally, methanol oxidation at the cathode leads to significant lowering of the efficiency in direct methanol fuel cells, which can be alleviated by use of methanol-tolerant catalysts. In this work, alternative carbon-supported platinum-alloy catalysts were investigated by physical methods. Second, methanol-tolerant ruthenium-selenide catalysts were characterized by physical and electrochemical methods. Besides V–i characteristics and electrochemical impedance spectroscopy as electrochemical methods, physical methods such as X-ray photoelectron spectroscopy, nitrogen adsorption, porosimetry by mercury intrusion and temperature programmed reduction are used to characterize the catalysts. The electrochemical characterization yields information about properties and behavior of the catalyst. In contrast to platinum a significantly different hydrophobic behavior of the RuSe/C catalysts is found. Low open circuit voltage values measured for RuSe/C indicate an effect on both electrodes. The anode reaction was also influenced by the different cathode catalysts. As a result of the formation of H₂O₂ at the cathode, which passes through the membrane from cathode to anode side, a mixed anode potential is formed. By comparing RuSe/C catalysts before and after electrochemical stressing, changes of the catalysts are determined. Postmortem surface analysis (by X-ray photoelectron spectroscopy) revealed that catalyst composition and MEA structure changed during electrochemical stressing. During fuel cell operation selenium oxide is removed from the surface of the catalysts to a large extent. Additionally, a segregation effect of selenium in RuSe to the surface is identified.     

Investigation of fuel and media flexible laminar flow-based fuel cells

We investigate the performance of air-breathing laminar flow-based fuel cells (LFFCs) operated with five different fuels (formic acid, methanol, ethanol, hydrazine, and sodium borohydride) in either acidic or alkaline media. The membraneless LFFC architecture enables interchangeable operation with different fuel and media combinations that are only limited by the actual anode catalyst used. Furthermore, operating under alkaline conditions significantly improves methanol and ethanol oxidation kinetics and stabilizes sodium borohydride. LFFCs operated with hydrazine and sodium borohydride as fuels exhibit power densities of 80 and 101 mW/cm², respectively. To optimize anode performance, particularly for ethanol electro-oxidation, we introduced a hydrogen cathode to the membraneless LFFC design which renders the cell an ideal platform for anode investigation. Here, we highlight two simple diagnostic methods, in situ single electrode studies and electrochemical impedance spectroscopy (EIS), for characterizing and optimizing the performance of a direct ethanol LFFC anode.     

The improved methanol tolerance using Pt/C in cathode of direct methanol fuel cell

Membrane electrode assemblies (MEA) were prepared using PtRu black and 60 wt.% carbon-supported platinum (Pt/C) as their anode and cathode catalysts, respectively. The cathode catalyst layers were fabricated using various amounts of Pt (0.5 mg cm⁻², 1.0 mg cm⁻², 2.0 mg cm⁻², and 3.0 mg cm⁻²). To study the effect of carbon support on performance, a MEA in which Pt black was used as the cathode catalyst was fabricated. In addition, the effect of methanol crossover on the Pt/C on the cathode side of a direct methanol fuel cell (DMFC) was investigated. The performance of the single cell that used Pt/C as the cathode catalyst was higher than single cell that used Pt black and this result was pronounced when highly concentrated methanol (above 2.0 M) was used as the fuel.     

Alternative cathodes based on iron phthalocyanine catalysts for mini- or micro-DMFC working at room temperature

Iron phthalocyanine based cathodes were prepared either by dispersion of FePc on carbon or by electropolymerization of aniline in presence of FeTsPc. The macrocycles based cathodes were compared to a classical commercial Pt/C cathode in a standard three-electrode electrochemical cell and under DMFC conditions at room temperature. It was shown that the molecular dispersion of FeTsPc into a PAni film greatly enhances the activity of the macrocycle catalyst towards oxygen reduction reaction (ORR). But, in the same time, the stability under DMFC conditions is drastically decreased compared to the stability obtained with a FePc/C electrode. It was suggested that this instability of the catalytic film was rather due to the release of the FeTsPc from the polymer than to the destruction of the macrocycle active centre. Even if iron phthalocyanine catalysts display total tolerance to methanol when the anode is fed with a 5 M methanol solution, the comparison between a PAni-FeTsPc/C cathode and a Pt/C cathode in DMFC working conditions is in favor of the Pt/C cathode, in term of maximum achieved power density. However, the ratio (platinum atoms per cm²/number of FeTsPc molecules per cm²) is close to 100, which allows to be optimistic for further enhancement of activity of polymer-FeTsPc electrodes. It was suggested that researches to develop new electron conductive polymers stable under oxidative environment and with a high doping capacity could be a direction to use platinum alternative cathode catalysts in DMFC technology.     

Realising a reference electrode in a polymer electrolyte fuel cell by laser ablation

This work presents a new concept for realising a reference electrode configuration in a PEM fuel cell by means of laser ablation. The laser beam is used to evaporate a small part of the electrode of a catalyst-coated membrane (CCM) to isolate the reference electrode from the active catalyst layer. This method enables the simultaneous ablation of the electrodes on both sides of the CCM because the membrane is transparent for the laser beam. Therefore, a smooth electrode edge without electrode misalignment can be realised. A test fuel cell was constructed which together with the ablated CCM enables the separation of the total cell losses during operation into the cathode, anode and membrane overpotentials in PEFC as well as in DMFC mode. The methanol tolerance of a selenium-modified ruthenium-based catalyst (RuSe _x ) was investigated under real fuel cell conditions by measuring polarisation curves, electrochemical impedance spectroscopy (EIS) and current interrupt measurements (CI).     

Na+ doping activates and stabilizes layered perovskite cathodes for high-performance fuel cells

A highly active mixed conductive cathode is required for solid oxide fuel cells (SOFCs) based on yttria-stabilized zirconia (YSZ) at reduced temperatures, which is one of the most important factors for their commercialization. Herein, we propose a Na⁺ doping strategy to activate and stabilize the triple-conducting (H⁺/O²⁻/e⁻) layered perovskite oxide of representative NdBa_0.5Sr_0.5Co_1.5Fe_0.5O_5+δ (NBSCF) for high-performance YSZ fuel cells. The results show that Na⁺ doping enhances the electrochemical properties of the NBSCF cathode, with polarization impedance decreasing from 0.105 to 0.080 Ω cm² at 750 °C and output power increasing from 946.05 to 1435.75 mW cm⁻² at 800 °C. Furthermore, high-temperature XRD (HT-XRD) and the oxygen temperature-programmed desorption (O₂-TPD) further confirm that Na⁺ doping can improve the structural stability of NBSCF. The single cell with a Na-doped NBSCF cathode showed no degradation of current density for more than 120 h at 700 °C and exhibited good stability. This work demonstrates the promise of Na⁺ doping for layered perovskite cathodes and an effective way to promote fuel cell performance.     

Alkaline direct methanol fuel cell based on a novel anion-exchange composite polymer membrane

The anion-exchange composite polymer membrane based on quaterized poly(vinyl alcohol)/poly(epichlorohydrin) (designated as Q-PVA/PECH) was prepared by a solution casting method and a quaternization process. The characteristic properties of the Q-PVA/PECH anion-exchange composite polymer membranes were investigated by scanning electron microscopy, thermal gravimetric analysis, micro-Raman spectroscopy, and AC impedance method. Alkaline direct methanol fuel cells (ADMFC) comprised Q-PVA/PECH anion-exchange composite polymer membranes were assembled and examined. Experimental results indicate that an alkaline DMFC employing an inexpensive non-perfluorinated Q-PVA/PECH composite polymer membrane shows excellent electrochemical performances. The peak power densities of the DMFC using 4 M KOH + 1 M CH₃OH, 2 M CH₃OH, and 4 M CH₃OH fuels are 17.22, 22.30, and 20.81 mW cm⁻², respectively, under ambient conditions. The Q-PVA/PECH composite polymer membrane appears as a viable candidate for use in an ADMFC.     

Effect of anode and cathode flow field depths on the performance of liquid feed direct methanol fuel cells (DMFCs)

The effect of the anode and cathode flow field depths on the performance of a single cell Direct methanol fuel cell (DMFC) of 45 cm² active area were experimentally investigated. Double serpentine flow fields (DSFFs) with varying channel depth namely, 0.2, 0.4, 0.6, 0.8, and 1 mm but with fixed channel and rib width each of 1 mm on both anode and cathode were designed, fabricated, and tested. The experimental study involved measurement of pressure drops across anode and cathode flow field plates, polarization, and carbon dioxide concentration measurements at various current densities. The mass transport at both anode and cathode were found to increase with increase in pressure drop across the flow field on account of reduced channel depth from 1.0 to 0.4 mm at all current densities. However, further decrease to a channel depth of 0.2 mm was found to be counter-productive with different phenomena operating on either side viz., increased CO₂ slug length on the anode flow channel and increased methanol crossover on the cathode side. Hence, the maximum performance for DMFCs was observed for a channel depth of 0.4 mm on anode and cathode flow fields. A decrease in flow field channel depth at cathode was found to increase the methanol crossover due to convective mass transfer effect.     

Distribution profile of water and suppression of methanol crossover in sulfonated polyimide electrolyte membrane for direct methanol fuel cells

We have developed novel cross-linked sulfonated polyimide (c-SPI) membrane as an electrolyte for direct methanol fuel cells (DMFCs). When the DMFC using the c-SPI membrane (thickness = 155 μm), Pt-Ru dispersed on carbon black (Pt-Ru/CB) anode and Pt/CB cathode with a Nafion^® ionomer was operated at 80 °C and 0.1 A cm⁻² with 1 M CH₃OH and oxygen (oxidant), the methanol crossover rate, j(CH₃OH), was suppressed to about 1/2 compared with that of the Nafion^® 117 membrane (thickness = 180 μm) with the same electrodes. It was found for both cells that the j(CH₃OH) was not so small as expected from the membrane thickness. In order to obtain a clue for the suppression of j(CH₃OH), the distribution profiles of water (containing CH₃OH) in thickness direction were investigated by measuring the specific resistances (ρ) between Pt probes inserted into the electrolyte membrane. Values of ρ at the anode side were low irrespective of the discharge current density, because such a part of the membrane was humidified thoroughly by liquid water (1 M CH₃OH) allowing free penetration of CH₃OH into the swollen polymer. In contrast, the values of ρ at the cathode side were high at the low current density due to drying of the membrane contacting with oxidant gas (O₂ or air) in low humidity. We have succeeded to suppress the j(CH₃OH) further (about 1/2 at 0.2 A cm⁻²) by using bilayer c-SPI, having a low ion exchanging (low swelling) barrier layer at the anode side without increasing the ohmic resistance, compared with that of the single c-SPI.     

Investigation of direct methanol fuel cell performance of sulfonated polyimide membrane

Sulfonated polyimide (SPI) membranes have been evaluated as electrolyte membranes in direct methanol fuel cells (DMFCs). The membrane-electrode assembly (MEA) was made by hot-pressing the membrane, an anode and a cathode, catalyzed with PtRu/CB (PtRu dispersed on carbon black) and Pt/CB bound with Nafion^® ionomer, respectively. The performance of the cell based on SPI was compared with that of Nafion^® 112 in various operation conditions such as cell temperature (T_cell), cathode relative humidity (RH), and methanol concentration (C_MeOH). The methanol crossover at the cell based on SPI was a half of Nafion^® 112, resulting in the improved cell efficiency. Advantage of the use of SPI became much distinctive from the conventional Nafion^® 112 when the DMFC was operated at a higher T_cell or a higher C_MeOH.     

The use of the heteropoly acids, H3PMo12O40 and H3PW12O40, for the enhanced electrochemical oxidation of methanol for direct methanol fuel cells

Polarization and electrochemical impedance spectroscopy experiments were performed on a direct methanol fuel cell (DMFC) incorporating the heteropoly acids (HPAs) phosphomolybdic acid, H₃PMo₁₂O₄₀, (HPMo) or phosphotungstic acid, H₃PW₁₂O₄₀, (HPW) in the anode Pt/C catalyst layer. Both HPW-Pt and HPMo-Pt showed higher performance than the Pt control at 30 psig of backpressure and at ambient pressure. Anodic polarizations were also performed, and Tafel slopes were extracted from the data between 0.25 V and 0.5 V. At 30 psig, Tafel slopes of 133 mV/dec, 146 mV/dec, and 161 mV/dec were found for HPW-Pt, HPMo-Pt and the Pt control, respectively. At 0 psig, the Tafel slopes were 172 mV/dec, 178 mV/dec, and 188 mV/dec for HPW-Pt, HPMo-Pt and the Pt control. An equivalent circuit model, which incorporated constant phase elements (CPEs), was used to model the impedance data. From the impedance model it was found that the incorporation of HPAs into the catalyst layer resulted in a reduction in the resistances to charge transfer. This shows that these two heteropoly acids do act as co-catalysts with platinum for methanol electrooxidation.