Development and electrochemical studies of gas diffusion electrodes for polymer electrolyte fuel cells

Electrochemical studies on low catalyst loading gas diffusion electrodes for polymer electrolyte fuel cells are reported. The best performance is obtained with an electrode formed from 20 wt% Pt/C, 0.4 mg Pt cm^–2 and 1.1 mg Nafion^® cm^–2 in the catalyst layer and 15% PTFE in a diffusion layer of 50 µm thickness, for both the cathode and the anode. However, it is also observed that the platinum requirement can be diminished to values close to 0.2 mg Pt cm^–2 in the cathode and 0.1 mg pt cm^–2 in the anode, without appreciably affecting the good characteristics of the fuel cell response. The experimental fuel cell data were analysed using theoretical models of the electrode structure and of the fuel cell system. It is seen that most of the electrode systems present limiting currents and some also show linear diffusion components arising from diffusion limitations in the gas channels and/or in the thin film of electrolyte covering the catalyst particles.     

Effects of the Diffusion Layer Characteristics on the Performance of Polymer Electrolyte Fuel Cell Electrodes

Several carbon blacks and graphite were investigated as candidates for diffusion layer preparation in polymer electrolyte fuel cell electrodes (PEFC). Single cell electrochemical characterizations under different working cell conditions were carried out on the electrodes by varying the kind of carbon in the diffusion layer. An improvement in cell performance was found by using Shawinigan Acetylene Black (SAB) as carbon, resulting in a measured power density of about 360 mW cm^–2 in H₂/air operation at 70°C and 1/1 bar. Pore size distribution and scanning electron microscopy analyses were carried out to help the understanding of the different behaviour of the investigated carbon diffusion layers.     

Influence of the structure in low-Pt loading electrodes for polymer electrolyte fuel cells

The influence of the structure and composition of the electrodes on a polymer electrolyte fuel cell (PEFC) performance has been investigated. Electrodes have been prepared by varying the composition of diffusion and/or catalyst layer. Improvements have been obtained by introducing a hydrophobic carbon layer between the carbon paper and the catalyst layer for the gas diffusion backing. High performance has been achieved with low Pt-loading electrodes (0.15 mg/cm²) by including the ionomer Nafion in the catalyst ink. Electrodes have been characterized by SEM-EDX analyses and electrochemical tests in a 50 cm² single cell.     

An oxygen electrode for air-consuming proton exchange membrane fuel cells for transportation applications

Electrodes for air-driven PEMFCs for transport applications have been developed. The structure of the electrodes has been specifically adapted to run with air as oxidant under near atmospheric pressure; such electrodes can be manufactured using conventional industrial methods and be easily scaled up. The technology has been demonstrated on a 50 cm² electrode area, assembled together with a Nafion® 117 membrane. Electrodes with different platinum loading, namely 0.4 and 0.2 mg Pt cm^–2, have been the subject of long duration tests which show a slow degradation of the cell performance. With air as oxidant at 180 kPa absolute pressure, 80°C as cell temperature and Nafion® 117 as membrane, a power density of 350 mW cm^–2 has been obtained.     

Cathodes for chlorate electrolysis with nanocrystalline Ti–Ru–Fe–O catalyst

Cathodes for chlorate electrolysis were prepared by mixing nanocrystalline Ti–Ru–Fe–O catalyst powder with small amounts of Teflon and subsequent hot pressing on a carbon–Teflon sublayer. Initially, the electrode materials were characterized by SEM, EDX, XRD and BET measurements. The behaviour of electrodes with catalyst loadings from 300 mg cm^–2 reduced to 10 mg cm^–2 was investigated in chlorate electrolyte with pH 6.5 and in part, for comparison, in 1 M sodium hydroxide solution at 70 C. Several methods have been used: cyclic voltammetry for the determination of double layer capacitance, Tafel plot analysis, cathodic potentiodynamic polarization and potentiostatic tests at i = –250 mA cm^–2. The as-milled catalyst powder electrodes showed a high activity for the HER in chlorate electrolyte particularly expressed in low overpotentials of about 580 mV at –250 mA cm^–2 for catalyst loadings down to 20 mg cm^–2 and high double layer capacitances in the freshly prepared state. These electrodes show increased activity at low polarization. The long-term stability during electrolysis was also analysed.     

Direct methanol alkaline fuel cells with catalysed anion exchange membrane electrodes

Membrane electrodes prepared by chemical deposition of platinum directly onto the anion exchange membrane electrolyte were tested in direct methanol alkaline fuel cells. Data on the cell voltage against current density performance and anode potentials are reported. The relatively low fuel cell performance was probably due to the low active surface area of Pt deposits on the membrane comparing to other membrane electrode assembly (MEA) fabrication methods. However, the catalysed membrane electrode showed good performance for oxygen reduction. A reduction in cell internal resistance was also obtained for the catalysed membrane electrode. By combining the catalysed membrane electrodes with a catalysed mesh, maximum current density of 98 mA cm^–2 and peak power density of 18 mW cm^–2 were achieved.     

Influence of the PTFE content in the diffusion layer of low-Pt loading electrodes for polymer electrolyte fuel cells

The influence of the structure and composition of the diffusion layer on polymer electrolyte fuel cell (PEFC) cathode performance was investigated. Electrodes were prepared with different poly-tetrafluoroethylene (PTFE) content in the diffusion layer and maintaining a constant composition for the catalytic layer with a low-Pt loading (0.11 mg cm⁻²). Electrodes were characterized by Hg-intrusion porosimetry, scanning electron microscopy and electrochemical techniques (cyclic voltammetry, galvanostatic polarization and ac-impedance spectroscopy).     

High-performance carbon electrodes for acid methanol—air fuel cells

High-performance, Teflon-bonded carbon electrodes, catalysed with highly dispersed platinum metal, have been developed for oxygen reduction in H₂SO₄. Surface-treated Vulcan XC-72 carbon has been used as the substrate material. The electrodes can be loaded with current densities of 1.1 A cm^–2 intermittently and 900 mA cm^–2 for extended periods without serious degradation. The performance of these electrodes in the presence of methanol has also been examined.     

Multi-variable optimization of PEMFC cathodes using an agglomerate model

A comprehensive numerical framework for cathode electrode design is presented and applied to predict the catalyst layer and the gas diffusion layer parameters that lead to an optimal electrode performance at different operating conditions. The design and optimization framework couples an agglomerate cathode catalyst layer model to a numerical gradient-based optimization algorithm. The set of optimal parameters is obtained by solving a multi-variable optimization problem. The parameters are the catalyst layer platinum loading, platinum to carbon ratio, amount of electrolyte in the agglomerate and the gas diffusion layer porosity. The results show that the optimal catalyst layer composition and gas diffusion layer porosity depend on operating conditions. At low current densities, performance is mainly improved by increasing platinum loading to values above 1 mg cm⁻², moderate values of electrolyte volume fraction, 0.5, and low porosity, 0.1. At higher current densities, performance is improved by reducing the platinum loading to values below 0.35 mg cm⁻² and increasing both electrolyte volume fraction, 0.55, and porosity 0.32. The underlying improvements due to the optimized compositions are analyzed in terms of the spatial distribution of the various overpotentials, and the effect of the agglomerate structure parameters (radius and electrolyte film) are investigated. The paper closes with a discussion of the optimized composition obtained in this study in the context of available experimental data. The analysis suggests that reducing the solid phase volume fraction inside the catalyst layer might lead to improved electrode performance.     

Performance and thermodynamic properties of Na-Sn and Na-Pb molten alloy electrodes for alkali metal thermoelectric converter (AMTEC)

An alkali metal thermoelectric converter (AMTEC) testing cell was set up, and run with molten sodium-tin (Na-Sn) and sodium-lead (Na-Pb) alloy cathodes. The Na activity, the partial molar enthalpy and partial molar entropy of sodium in molten Na-Sn and Na-Pb alloys have been determined, using a Na concentration cell: Na(1) I beta-alumina Na-Me(1), where Me= Sn or Pb. The thermodynamic results of these investigations agree with those of other authors. The electric performance of these Na-Me alloy electrodes of different Na concentration and temperatures is described, measuring current-voltage characteristics and a.c. impedance in the AMTEC test cell. The power density of the AMTEC cell with molten alloy cathodes decreases with increasing Na concentration, with the Na concentrations in molten alloys varying from 0.5 to 15 mol%. Maximum power densities of 0.21 to 0.15 W cm^–2 at 700°C for Na-Sn molten electrodes, and 0.30 to 0.15 W cm^–2 for Na-Pb molten electrodes have been obtained. The a.c. impedance data demonstrated that the molten alloy electrodes have a smaller cell resistance, 0.3–0.35 S2 cm^–2 at 700°C after 10–20 h. Comparison with the sputtered thin, porous film electrodes, showed that the contact resistance between electrode and surface of beta-alumina plays an important role on enhancing cell power density. At 700°C the power density of an AMTEC cell with the molten Na-Pb alloy electrode can be raised to values of about 0.2 W cm eat current densities of 0.8 A cm^–2, but at cell voltages not exceeding 0.2V. A model for the theoretical efficiency of the AMTEC cell with molten Na metal electrodes is also presented.     

Water diffusion coefficients during copper electropolishing

Cu electropolishing was studied using a rotating disc electrode in a variety of phosphoric acid-based electrolytes, including several with ethanol and other species added as diluents. Diluents allow a wider range of water concentrations and electrolyte viscosities to be accessed and also reduce the removal rate during Cu electropolishing, simplifying possible application to damascene processing. Transient and steady state currents in the mass transfer limited regime are shown to depend on both the number of water acceptor molecules associated with each dissolving Cu ion and on the effective diffusion coefficient of water. Transient analysis samples the bulk transport properties, whereas steady state analysis integrates them through the diffusion layer. Assuming that the effective diffusion coefficients appropriate to transient and steady state behavior are the same, about one water molecule is associated with each dissolving Cu ion. This analysis yields effective diffusion coefficients for water on the order of 10^–9cm²s^–1. However, the data is also consistent with an assumption that six water molecules are associated with each dissolving Cu ion, but the effective diffusion coefficient appropriate for a Levich analysis is somewhat lower than that in the bulk electrolyte. This analysis yields effective diffusion coefficients for water on the order of 10^–8–10^–7cm²s^–1. The latter interpretation, that six water molecules are associated with each dissolving Cu ion, appears more likely since it provides almost exact agreement with the effective diffusion coefficient reported previously by Vidal and West. In combination with previously published impedance results ruling out a salt film mechanism, the good agreement between the transient and steady state analyses confirm that water is the acceptor species that complexes dissolving Cu ions in phosphoric acid-based electropolishing baths.     

Effect of gas diffusion layer compression on the performance in a proton exchange membrane fuel cell

This study investigates the gas permeability, bulk density, thickness and conductivity of two types of gas diffusion layer (OC14, NC14) as a function of the compressed thickness. The compression of a gas diffusion layer reduces gas permeability and contact resistance. The performance is measured using a single proton exchange membrane fuel cell (PEMFC) with an active area of 25 cm². The results provide an optimum value of compression ratio that maximizes the cell performance. For OC14 the optimum compression ratio is about 64%, whereas for NC14 it is 59%. The best performances are 375 mA/cm² and 296 mA/cm² at 0.7 V, respectively. These results concerning the balance between compression and performance provide vital information for the fabrication of stacks and support for industrial applications.     

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.     

In situ grown carbon nanotubes on carbon paper as integrated gas diffusion and catalyst layer for proton exchange membrane fuel cells

In situ grown carbon nanotubes (CNTs) on carbon paper as an integrated gas diffusion layer (GDL) and catalyst layer (CL) were developed for proton exchange membrane fuel cell (PEMFC) applications. The effect of their structure and morphology on cell performance was investigated under real PEMFC conditions. The in situ grown CNT layers on carbon paper showed a tunable structure under different growth processes. Scanning electron microscopy (SEM) and Brunauer–Emmett–Teller (BET) demonstrated that the CNT layers are able to provide extremely high surface area and porosity to serve as both the GDL and the CL simultaneously. This in situ grown CNT support layer can provide enhanced Pt utilization compared with the carbon black and free-standing CNT support layers. An optimum maximum power density of 670 mW cm⁻² was obtained from the CNT layer grown under 20 cm³ min⁻¹ C₂H₄ flow with 0.04 mg cm⁻² Pt sputter-deposited at the cathode. Furthermore, electrochemical impedance spectroscopy (EIS) results confirmed that the in situ grown CNT layer can provide both enhanced charge transfer and mass transport properties for the Pt/CNT-based electrode as an integrated GDL and CL, in comparison with previously reported Pt/CNT-based electrodes with a VXC72R-based GDL and a Pt/CNT-based CL. Therefore, this in situ grown CNT layer shows a great potential for the improvement of electrode structure and configuration for PEMFC applications.     

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 .     

Electrochemical oxidation of manganese(II) at a platinum electrode

Electrochemical oxidation of Mn²⁺ in sulphuric acid to form MnO₂ was studied using stationary and rotating platinum/platinum ring-disc electrodes. It appears that nucleation of MnO₂ is governed by an equilibrium involving a Mn(III) intermediate. Growth of MnO₂ involves the reduction of MnO₂ surfaces by Mn²⁺ ions in the solution to form MnOOH intermediates. The subsequent electrochemical oxidation of MnOOH releases a hydrogen ion and results in the formation of MnO₂. The rate constant of MnOOH oxidation to MnO₂ was estimated to be 40 s^–1. With a sufficient supply of Mn²⁺ ions, a layer of MnOOH is built up and the in-solid diffusion of hydrogen ions becomes the ratedetermining-step. With a low Mn²⁺ concentration, diffusion of Mn²⁺ ions from bulk electrolyte to the MnO₂/electrolyte interface is a factor controlling the growth of MnO₂. The activation energy and the pre-exponential term of the diffusion coefficient of Mn²⁺ in 0.5m sulphuric acid were determined to be 44.8 kJ mol^–1 and 100 cm² s^–1, respectively.     

Oxygen electroreduction in perfluorinated sulphonyl imides

The electroreduction of oxygen in perfluorinated sulphonyl imides has been studied with the emphasis on the identification of alternate acid electrolytes which could replace the presently used phosphoric acid as an electrolyte in H₂–O₂ fuel cells. The activity for oxygen reduction on smooth platinum and gas-fed, high surface area platinum-catalysed electrodes (10% platinum loading on XC-72 carbon support) has been examined. The polarization of the air cathode in the micro-fuel cell in bis(trifluoromethanesulphonyl)imide is 40 mV more positive compared to phosphoric acid at 100 mA cm^–2, presumably due to the increased solubility of oxygen and lower tendency of bis(trifluoromethanesulphonyl)imide to adsorb on the platinum catalyst. The related bis(fluorosulphonyl)imide is unstable in water and the hydrolysis products adsorb strongly on the catalytic sites, resulting in poor performance.     

Carbon electrodes with phthalocyanine catalyst in acid medium

The catalytic properties of polymeric phthalocyanines with Fe and Co as central atoms for the electroreduction of oxygen in 0.5–2.3m H₂SO₄ were studied. No noticeable dependence of the electrode potential on the concentration of H₂SO₄ was found. The electroactivity of the catalyst with a central Fe atom undergoes considerable deterioration under the given conditions, whereas the stability of the catalyst with a central Co atom is very good and the potential of an electrode containing 30% catalyst in the active mass is 100 mV more positive than that of an electrode with 13% platinum, both at 40 mA cm^–2. The electrode performance depends markedly on the sort of carbon substrate, showing a parallelism with respect to oxygen electrodes in alkaline medium. The gold mesh current collector can be replaced by the addition of carbon black to the active layer.     

Electrochemical nucleation and growth of copper on chromium-plated electrodes

Nucleation and growth of copper electrodeposited on chromium plated electrodes in copper sulfate electrolytes were examined, focusing on the influence of prior Cr plating conditions on the nucleation density and growth kinetics of the copper electrodeposits. The Cr-plated electrodes were made by electrodeposition of Cr on copper sheets for 2 to 60 s at 0.1 A cm^–2 in CrO₃ 350 g L^–1 + H₂SO₄ 3.5 g L^–1. Copper was then electrodeposited onto the Cr-plated electrode under potentiostatic conditions. Copper initially nucleated and grew according to a three-dimensional diffusion controlled progressive nucleation process, and later according to an instantaneous nucleation process. The period during which copper nucleation is controlled by the diffusion controlled progressive nucleation process decreases with increasing Cr plating time. The nucleation density of copper was extremely high on the 2 s Cr-plated electrode, producing an extremely fine and uniform electrodeposit. However, on the 4 s Cr-plated electrode, the nucleation density of copper significantly reduced to one hundredth of that on the 2 s Cr-plated electrode, and then decreased slightly with increasing Cr plating time (thickness of Cr layer). These results appear to be associated with the IR drop across the Cr layer, including the surface Cr oxide/hydroxide film (termed the cathode film), which significantly reduces the driving force for the electrodeposition of copper under potentiostatic plating conditions.     

Study of a high power density sodium polysulfide/bromine energy storage cell

Nickel catalyst supported on carbon was made by reduction of nickelous nitrate with hydrogen at high temperature. Ni/C catalyst characterization was carried out by XRD. It was found that the crystal phase of NiS and NiS₂ appeared in the impregnated catalyst. Ni/C and Pt/C catalysts gave high performance as the positive and negative electrodes of a sodium polysulfide/bromine energy storage cell, respectively. The overpotentials of the positive and negative electrodes were investigated. The effect of the electrocatalyst loading and operating temperature on the charge and discharge performance of the cell was investigated. A power density of up to 0.64 W cm^–2 (V = 1.07 V) was obtained in this energy storage cell. A cell potential efficiency of up to 88.2% was obtained when both charge and discharge current densities were 0.1 A cm^–2.