Performance of a direct methanol fuel cell

The performance of a direct methanol fuel cell based on a Nafion® solid polymer electrolyte membrane (SPE) is reported. The fuel cell utilizes a vaporized aqueous methanol fuel at a porous Pt–Ru–carbon catalyst anode. The effect of oxygen pressure, methanol/water vapour temperature and methanol concentration on the cell voltage and power output is described. A problem with the operation of the fuel cell with Nafion® proton conducting membranes is that of methanol crossover from the anode to the cathode through the polymer membrane. This causes a mixed potential at the cathode, can result in cathode flooding and represents a loss in fuel efficiency. To evaluate cell performance mathematical models are developed to predict the cell voltage, current density response of the fuel cell.     

A Solid-polymer Electrolyte Direct Methanol Fuel Cell with a Methanol-tolerant Cathode and its Mathematical Modelling

Solid-polymer electrolyte direct methanol fuel cells (SPE-DMFCs) employing carbon-supported Pt–Fe as oxygen-reduction catalyst to mitigate the effect of methanol on cathode performance while operating with oxygen or air have been assembled. These SPE-DMFCs provided maximum power densities of 250 and 120 mW cm^–2 at 85 °C on operating with oxygen and air, respectively. The polarization data for the SPE-DMFCs and their constituent electrodes have also been derived numerically employing a model based on phenomenological transport equations for the catalyst layer, diffusion layer and the membrane electrolyte.     

Investigation of Ternary Catalysts for Methanol Electrooxidation

The electrochemical oxidation of methanol was investigated on Pt–Ru–X ternary metallic catalysts (with X=Au, Co, Cu, Fe, Mo, Ni, Sn or W). The catalysts were prepared by electrochemical deposition and dispersed in a conductive three-dimensional matrix, an electronic conducting polymer, polyaniline (PAni). A comparative study of the behaviour of several ternary catalysts towards the electro-oxidation of methanol shows that PAni/Pt–Ru–Mo is the most efficient anode at potentials up to 500mV vs RHE. This latter ternary electrocatalyst leads to current densities up to 10 times higher than those measured with PAni/Pt–Ru in this potential range. Moreover, the catalyst appears to be stable for potentials lower than 550mV vs RHE. According to EDX analysis, the good behaviour of the Pt–Ru–Mo ternary catalyst seems to result from the presence of a small amount of the third metal, at an atomic ratio close to 5%. This set of encouraging results has also been confirmed by preliminary measurements in a single cell direct methanol fuel cell (DMFC) containing a home made PAni/Pt–Ru–Mo anode. The ternary catalyst leads to higher power densities than the PAni/Pt–Ru binary catalyst under the same experimental conditions.     

Optimization of operating parameters of a direct methanol fuel cell and physico-chemical investigation of catalyst–electrolyte interface

A physico-chemical investigation of catalyst–Nafion® electrolyte interface of a direct methanol fuel cell (DMFC), based on a Pt–Ru/C anode catalyst, was carried out by XRD, SEM-EDAX and TEM. No interaction between catalyst and electrolyte was detected and no significant interconnected network of Nafion micelles inside the composite catalyst layer was observed. The influence of some operating parameters on the performance of the DMFC was investigated. Optimal conditions were 2 M methanol, 5 atm cathode pressure and 2–3 atm anode pressure. Power densities of 110 and 160 mW cm⁻² were obtained for operation with air and oxygen, respectively, at temperatures of 95–100°C and with 1 mg cm⁻² Pt loading.     

Iron(III) tetramethoxyphenylporphyrin(FeTMPP) as methanol tolerant electrocatalyst for oxygen reduction in direct methanol fuel cells

Carbon supported iron (III) tetramethoxyphenylporphyrin (FeTMPP) heat treated at 800°C under argon atmosphere was used as catalysts for the electroreduction of oxygen in direct methanol polybenzimidazole (PBI) polymer electrolyte fuel cells that were operated at 150°C. The electrode structure was optimized in terms of the composition of PTFE, polymer electrolyte and carbon-supported FeTMPP catalyst loading. The effect of methanol permeation from anode to cathode on performance of the FeTMPP electrodes was examined using spectroscopic techniques, such as on line mass spectroscopy (MS), on line Fourier transform infrared (FTIR) spectroscopy and conventional polarization curve measurements under fuel cell operating condition. The results show that carbon supported FeTMPP heat treated at 800°C is methanol tolerant and active catalyst for the oxygen reduction in a direct methanol PBI fuel cell. The best cathode performance under optimal condition corresponded to a potent ial reached of 0.6V vs RHE at a current density of 900 mAcm–2.     

Enhancement of the electrooxidation of ethanol on a Pt–PEM electrode modified by tin. Part I: Half cell study

The direct platinisation of a solid polymer electrolyte (Nafion^® membrane) was realized by chemical reduction of a platinum salt. The Pt–PEM electrodes thus obtained were modified by tin to improve the electrocatalytic activity towards the electrooxidation of ethanol. The Pt–PEM and Pt–Sn–PEM electrodes were characterized by TEM, EDX and XRD analysis, cyclic voltammetry, and their polarisation curves for the electrooxidation of ethanol were determined under quasisteady state conditions.     

Direct Methanol Fuel Cells Using Thermally Catalysed Ti Mesh

Characterisation of a direct methanol fuel cell using an anode fabricated by thermal decomposition from Pt–Ru chloro-complex on Ti mesh is described. The polarisation characteristic of the resultant membrane electrode assembly is compared with that of a conventional MEA with an anode, consisting of a catalyst layer, a microporous layer and a wet-proof-treated carbon paper. Electrode characterisation was carried out using XRD, SEM and EDX analyses. In 1 m methanol solution, the MEA with the catalysed Ti mesh anode gave a power performance comparable with that of the conventional anode at 90 °C. However, in 0.5 m methanol solution the former showed much higher power density than the latter, indicating high utilisation of methanol fuel.     

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 .     

Synergetic effect of combined use of Cu–ZnO–Al2O3 and Pt–Al2O3 for the steam reforming of methanol

Commercial Cu–ZnO–Al₂O₃ catalysts are used widely for steam reforming of methanol. However, the reforming reactions should be modified to avoid fuel cell catalyst poisoning originated from carbon monoxide. The modification was implemented by mixing the Cu–ZnO–Al₂O₃ catalyst with Pt–Al₂O₃ catalyst. The Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalyst mixture created a synergetic effect because the methanol decomposition and the water–gas shift reactions occurred simultaneously over nearby Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalysts in the mixture. A methanol conversion of 96.4% was obtained and carbon monoxide was not detected from the reforming reaction when the Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalyst mixture was used.     

Optimization of platinum dispersion in Pt–PEM electrodes: application to the electrooxidation of ethanol

Nafion® can be used as a solid polymer electrolyte in a PEM fuel cell. Direct platinization of the membrane was realized by chemical reduction of a platinum compound. The platinization procedure was modified to enhance the roughness factor and thus to improve the electrocatalytic activity towards ethanol electrooxidation. The Pt–PEM electrodes were characterized by TEM, atomic absorption analysis, cyclic voltammetry and their polarization curves for ethanol electrooxidation.     

CO and CO/H2 electrooxidation on carbon supported Pt–Ru catalyst in phosphotungstic acid (H3PW12O40) electrolyte

An electrode-kinetic study of the oxidation of CO and CO/H2 mixtures on a Pt–Ru/C catalyst was carried out in phosphotungstic acid (PWA) electrolyte. The influence of temperature, CO partial pressure and proton concentration on the electrochemical oxidation rate was investigated. An apparent activation energy of about 50kJmol–1 was found for CO oxidation at 0.6V vs NHE. Fractional reaction orders close to 0.5 and –0.4 with respect to carbon monoxide and proton concentration, respectively, were observed. Tafel slopes were close to 136mVdec–1 at 70°C for both CO and CO/H2 oxidation. The PWA electrolyte appeared to promote the methanol electrooxidation by increasing the rate of water discharge at the electrode.     

Development and operation of a 150 W air-feed direct methanol fuel cell stack

A five-cell 150 W air-feed direct methanol fuel cell (DMFC) stack was demonstrated. The DMFC cells employed Nafion 117^® as a solid polymer electrolyte membrane and high surface area carbon supported Pt-Ru and Pt catalysts for methanol electrooxidation and oxygen reduction, respectively. Stainless steel-based stack housing and bipolar plates were utilized. Electrodes with a 225 cm² geometrical area were manufactured by a doctor-blade technique. An average power density of about 140 mW cm^–2 was obtained at 110 °C in the presence of 1 M methanol and 3 atm air feed. A small area graphite single cell (5 cm²) based on the same membrane electrode assembly (MEA) gave a power density of 180 mW cm^–2 under similar operating conditions. This difference is ascribed to the larger internal resistance of the stack and to non-homogeneous reactant distribution. A small loss of performance was observed at high current densities after one month of discontinuous stack operation.     

Synthesis of sulfated ZrO2/MWCNT composites as new supports of Pt catalysts for direct methanol fuel cell application

Sulfated zirconia supported on multi-walled carbon nanotubes as new supports of Pt catalyst (Pt–S-ZrO₂/MWCNT) was synthesized with aims to enhance electron and proton conductivity and also catalytic activity of Pt electrocatalyst in terms of larger concentrations of ionizable OH groups on surfaces. Fourier transform infrared spectroscopy analysis shows that the sample surfaces were modified with sulfate. Transmission electron microscopy results show that the Pt and sulfated ZrO₂ particles dispersed relatively uniformly on the surface of the multi-walled carbon nanotube. X-ray diffraction shows that S-ZrO₂ and Pt coexist in the Pt–S-ZrO₂/MWCNT composites and S-ZrO₂ has no effect on the crystalline lattice of Pt. Pt–S-ZrO₂/MWCNT catalyst was evaluated in terms of the electrochemical activity for methanol electro-oxidation using cyclic voltammetry, steady-state polarization experiments and electrochemical impedance spectroscopy technique at room temperature. Pt–S-ZrO₂/MWCNT catalyst show higher catalytic activity for methanol electro-oxidation compared with Pt catalyst on non-sulfated ZrO₂/MWCNT support and commercial Pt/C (E-TEK).     

Influence of preparation process of MEA with mesocarbon microbeads supported Pt–Ru catalysts on methanol electrooxidation

The effects of mesocarbon microbeads support for platinum–ruthenium (Pt–Ru) catalysts on anode performance of the direct methanol fuel cell (DMFC) were investigated. Polarization characteristics of the anode electrode were low due to the fast rate of mass transport in the electrode. The effects of the Nafion^® content in the catalyst, the MEA hot press condition, the cell operation temperature and methanol concentration on the polarization curves of the anode were also investigated.     

A thin-film/agglomerate model of a proton-exchange-membrane fuel cell cathode catalyst layer with consideration of solid-polymer-electrolyte distribution

A thin-film/agglomerate model for the cathode part of a proton-exchange-membrane fuel cell is developed. Parameter estimation is employed to determine the exchange current density in the catalyst layer, proton conductivity of the recast ionomer, and oxygen diffusivity in the solid polymer electrolyte. The effects of catalyst and polymer electrolyte loadings in the catalyst layer on the cell performance are demonstrated using this model. The influence of polymer electrolyte distribution in the catalyst layer is correlated with the oxygen diffusion and proton migration rates within the electrolyte. It is found that proton migration in the polymer electrolyte is the dominant factor for cell current density under normal operating conditions. A better cell performance is achieved by a concentrated polymer electrolyte near the catalyst layer/membrane interface.     

Effect of carbon-supported and unsupported Pt–Ru anodes on the performance of solid-polymer-electrolyte direct methanol fuel cells

The structure, chemistry and morphology of commercially available carbon-supported and unsupported Pt–Ru catalysts are investigated by X-ray diffraction, energy-dispersive analysis by X-rays and electron microscopy. The catalytic activities of these materials towards electrooxidation of methanol in solid-polymer-electrolyte direct methanol fuel cells have been investigated at 90C and 130C with varying amounts of Nafion ionomer in the catalytic layer. The unsupported Pt–Ru catalyst exhibits higher performance with lower activation-control and mass-polarization losses in relation to the carbon-supported catalyst.On leave from the     

Carbon monoxide electrooxidation on porous Pt–Ru electrodes in sulphuric acid

CO electrooxidation on a Pt–Ru/C catalyst was investigated in sulphuric acid electrolyte. The physico-chemical properties of the Pt–Ru/C catalyst were studied by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The influence of temperature, CO partial pressure and proton concentration on the electrochemical oxidation rate was investigated by steady-state galvanostatic polarization measurements. The apparent activation energy decreased from 70 to 30kJmol–1 as the overpotential increased from 0.5 to 0.9V vs NHE. The reaction order with respect to carbon monoxide increased, passing from 0.4 to 1, with the increase of the overpotential from 0.5 to 0.7V vs NHE; a reaction order close to –1 with respect to the protonic concentration was observed, irrespective of the potential. Tafel slopes of about 136mVdec–1 were determined for oxidation of CO and CO/N2 mixtures.     

Simulation studies on the fuel electrode of a H2---O2 polymer electrolyte fuel cell

The macro-homogeneous porous electrode theory is used to develop a model which describes the catalyst layer of the hydrogen electrode formed by catalyst particles that are bonded to the membrane. The water transport in the catalyst layer and polymer electrolyte membrane is considered. The effects of catalyst layer structure parameters such as polymer volume fraction, catalyst layer thickness, platinum loading and reactant gas humidity as well as CO poison on the hydrogen electrode behavior are examined. The results show that the catalyst layer thickness has a significant effect on the electrode performance. A thicker catalyst layer will result in a larger ohmic voltage loss and higher catalyst cost. The optimal polymer volume fraction and catalyst layer thickness are 0.5 and 1.5–4 μm, respectively, for this electrode. An optimal platinum surface coverage on carbon need not exceed 20% (20 wt% Pt/C). Larger platinum coverage will increase the cost, but only slightly enhance the electrode performance.     

Platinum-based Alloys as oxygen–reduction Catalysts for Solid–Polymer–Electrolyte Direct Methanol Fuel Cells

Electrocatalytic activities of various carbon-supported platinum-based binary, namely, Pt–Co/C, Pt–Cr/C and Pt–Ni/C, and ternary, namely, Pt–Co–Cr/C and Pt–Co–Ni/C, alloy catalysts towards oxygen reduction in solid–polymer–electrolyte direct methanol fuel cells were investigated at 70°C and 90°C both at ambient and 2bar oxygen pressures. It was found that Pt–Co/C exhibits superior activity relative to Pt/C and other alloy catalysts.     

Reforming methanol to electricity in a high temperature PEM fuel cell

In this paper we demonstrate for the first time a compact power unit, where a methanol reforming catalyst is incorporated into the anode of a PEMFC. The proposed internal reforming methanol fuel cell (IRMFC) mainly comprises: (i) a H₃PO₄-imbibed polymer electrolyte based on aromatic polyethers bearing pyridine units, able to operate at 200 °C and (ii) a 200 °C active and with zero CO emissions Cu–Mn–O methanol reforming catalyst supported on copper foam. Methanol is being reformed inside the anode compartment of the fuel cell at 200 °C producing H₂, which is readily oxidized at the anode to produce electricity. The IRMFC showed promising electrochemical behavior and no signs of performance degradation for more than 72 h.