Analysis of high temperature polymer electrolyte membrane fuel cell electrodes using electrochemical impedance spectroscopy

An electrochemical impedance spectroscopy (EIS) study of electrodes in a phosphoric acid loaded polybenzimidazole (PBI) membrane fuel cell is reported. Using EIS, the effect of electrode parameters such as Pt catalyst wt%, acid doping in PBI and PTFE baesd electrodes and catalyst heat treatment on kinetic and mass transport characteristics is characterised. The influence of cell parameters of current load, temperature and oxidant gas on response is demonstrated and interpreted using an equivalent circuit model. For polarisable electrodes under small to medium steady-state current operation, the model was capable of identifying electrodes with the best kinetic or mass transport behaviour and classifying behaviour in terms of relative performance.     

Preparation of Raney–Ni gas diffusion electrode by filtration method for alkaline fuel cells

A novel filtration method for preparation of gas diffusion electrodes for fuel cells is proposed. This method, which is a modification of the conventional dry method, has the merits of both wet and dry techniques. The electrode performance is improved due to better structure, controlled hydrophobicity and less compaction. To compare the effectiveness of the method, Raney–Ni/PTFE anodes for use in a KOH fuel cell were made. Their electrochemical performance was compared with similar electrodes produced by the dry method by other research groups, under the same conditions. The filtration method electrodes performed better between temperatures of 25°C and 75°C. The electrode exhibited no significant degradation of activity in the first 180h at 100mAcm–2 anodic load.     

Dissolution and Migration of Platinum in PEMFCs Investigated for Start/Stop Cycling and High Potential Degradation

Dissolution and migration of platinum due to start/stop degradation and increased cathode potentials were studied for commercial membrane electrode assemblies (MEA). The chosen conditions closely mimic real situations in automotive operation. In start/stop tests, we observed a strongly enhanced platinum dissolution due to the dynamic interplay of repeated cell start‐up and consecutive normal fuel cell operation, which is related to platinum oxidation (start‐up) and reduction (normal operation) cycles. Consequently, the performed test protocols distinguish between dynamic and static load profiles. Electrochemical investigations before and after degradation monitor the loss in cell performance. Since electron microscopy offers the unique possibility to unravel and distinguish degradation due to carbon corrosion and agglomeration or platinum dissolution, a focus was set on this method. For the start/stop MEA pronounced platinum dissolution accompanied by the formation of large platinum precipitations in the membrane was found. Carbon corrosion was also observed, but did not lead to a significantly reduced porosity and loss in platinum dispersion. In contrast, the MEA which was exposed to high constant potentials exhibited severe damage to the 3D cathode structure due to carbon corrosion. However, no pronounced platinum dissolution was observed and only few Pt precipitations were found in the membrane itself.     

A study of PtRuO2 catalysts thermally formed on titanium mesh for methanol oxidation

Platinum-based catalysts, for the electro-oxidation of methanol, have been made by thermal decomposition of chloride precursors onto titanium mesh. The catalysed electrodes were successfully operated in acidic methanol electrolytes. Electrochemical characterisation has been carried out using cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic polarisations. A complete analysis of the electrochemical results showed that the preliminary performance of the catalysed titanium mesh was comparable to that achieved with carbon-supported PtRu catalysts. The catalysts formed on titanium mesh by thermal decomposition also exhibited dimensional stability. Catalysed titanium mesh therefore appears to be a promising alternative to carbon-supported catalysts for certain fuel cell applications.     

Characterization of membrane electrode assemblies in polymer electrolyte fuel cells using a.c. impedance spectroscopy

The most common methods used to characterize the electrochemical performance of fuel cells are to record current–voltage U(i) curves. However, separation of electrochemical and ohmic contributions to the U(i) characteristics requires additional experimental techniques. The application of electrochemical impedance spectra (EIS) is an approach to determine parameters which have proved to be indispensable for the development of fuel cell electrodes and membrane electrode assemblies (MEAs). This paper proves that it is possible to split the cell impedance into electrode impedances and electrolyte resistance by varying the operating conditions of the fuel cell (current load) and by simulation of the measured EIS with an equivalent circuit. Furthermore, integration in the current density domain of the individual impedance elements enables the calculation of the individual overpotentials in the fuel cell and the determination of the voltage loss fractions.     

低铂燃料电池氧还原催化剂的制备技术研究进展

低铂燃料电池催化剂铂载量低,在具有较高活性的同时能够极大地降低燃料电池的成本,因此,开发低铂燃料电池催化剂一直是燃料电池催化剂的重要研究方向。本文综述了低铂燃料电池催化剂的最新研究进展,对低铂燃料电池催化剂进行了分类,包含Pt基合金结构催化剂、Pt基核壳结构催化剂、Pt单原子层结构催化剂和Pt单原子催化剂等;详细介绍了几种低铂燃料电池催化剂的制备方法,主要包括有机溶胶法、电化学还原沉积法、气相沉积法、原子层沉积法、离子液体法、微波法,并对各自的优缺点进行了总结;重点强调了核壳结构电催化剂的制备方法,包括两步有机溶胶法、脉冲电沉积法、表面去合金化法、欠电位沉积法以及中空构型核壳结构催化剂的制备。最后指出可控制备具有高活性和高稳定性的低铂核壳结构催化剂是质子交换膜燃料电池实现商业化的重要研究方向。     

Scanning electron microscopic studies of porous carbon electrodes used in alkaline fuel cells

Multilayer, polytetrafluoroethylene (PTFE)-bonded gas diffusion-type electrodes were prepared by the rolling method. Changing the electrode structure and manufacturing method improved alkaline fuel cell performance. Activated carbon or carbon black was used as the support material, with platinum as a catalyst and nickel screen as the backing material. Double-layer electrodes possessed both active and diffusion layers on the backing layer. However, the single-layer electrodes had only the active layer on the backing layer. The electrodes were prepared by using different PTFE contents and platinum loadings. In this study the surface photographs of the electrodes were taken with a scanning electron microscope. Elemental analyses of the surface elements were performed by energy dispersive X-ray spectroscopy (EDXS). Electrodes having activated carbon on their surfaces were observed to possess a nonuniform and porous structure. These electrodes showed better performance than electrodes having carbon black, which presented a uniform and nonporous structure.     

Catalyst Degradation in High Temperature Proton Exchange Membrane Fuel Cells Based on Acid Doped Polybenzimidazole Membranes

Degradation of carbon supported platinum catalysts is a major failure mode for the long term durability of high temperature proton exchange membrane fuel cells based on phosphoric acid doped polybenzimidazole membranes. With Vulcan carbon black as a reference, thermally treated carbon black and multi‐walled carbon nanotubes were used as supports for electrode catalysts and evaluated in accelerated durability tests under potential cycling at 150 °C. Measurements of open circuit voltage, area specific resistance and hydrogen permeation through the membrane were carried out, indicating little contribution of the membrane degradation to the performance losses during the potential cycling tests. As the major mechanism of the fuel cell performance degradation, the electrochemical active area of the cathodic catalysts showed a steady decrease in the cyclic voltammetric measurements, which was also confirmed by the post TEM and XRD analysis. A strong dependence of the fuel cell performance degradation on the catalyst supports was observed. Graphitization of the carbon blacks improved the stability and catalyst durability though at the expense of a significant decrease in the specific surface area. Multi‐walled carbon nanotubes as catalyst supports showed further significant improvement in the catalyst and fuel cell durability.     

The effect of hydrophobicity in alkaline electrodes for passive DMFC

The effect of hydrophobicity in alkaline electrodes has been investigated in an effort to improve their performance in passive direct methanol fuel cells. Two approaches have been used to increase the hydrophobicity within the electrodes. One is using a more hydrophobic ionomer, and the other is introducing polytetrafluoroethylene (PTFE) into the catalyst layer. Two types of anion exchange ionomers with different hydrophobicity have been synthesized for this study. The effect of ion exchange capacity, ionic conductivity, and water uptake of the ionomers on the electrode performance has been studied using a half-cell test. The use of a hydrophobic ionomer resulted in enhanced cathode performance even though the ionic conductivity was lower than the more hydrophilic ionomer. Also, the addition of PTFE improved both the cathode and anode performance. The improved alkaline electrode performance was compared to a traditional acid electrode using Nafion as the ionomer. The performance increased threefold as a result of higher hydrophobicity in alkaline electrode.     

Electrochemical Evaluation of Porous Non‐Platinum Oxygen Reduction Catalysts for Polymer Electrolyte Fuel Cells

A porous non‐platinum electrocatalyst for the oxygen reduction reaction (ORR), obtained by pyrolysing a cobalt porphyrin precursor, was evaluated by electrochemical means. The reactivity of the non‐platinum ORR catalyst was investigated with a rotating disc electrode (RDE) experimental set up. RDE data were collected in an acidic electrolyte containing N₂, O₂, CO and under mixed reactant O₂/methanol conditions. The electrochemical performance of such‐obtained non‐platinum catalyst is discussed and compared to platinum‐based ORR catalysts. Based on the results collected here, we are able to propose and test possible proton exchange fuel cell (PEFC) operating conditions where non‐platinum ORR catalysts can be utilised. Direct methanol fuel cell (DMFC) data demonstrating a superior performance of the non‐platinum catalyst relative to platinum black, often perceived as the state‐of‐the‐art oxygen–reduction catalyst for the DMFC cathode is presented.     

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.     

Degradation of oxygen-depolarized Ag-based gas diffusion electrodes for chlor-alkali cells

Oxygen-depolarized cathodes consisting of gas-diffusion electrodes (GDEs) for electrolysis in a chlor-alkali cell at 90 °C were studied. The electrode design was based on a carbon-free catalyst and comprised of a mixture of micronized silver particles, a small amount of Hg and PTFE binder. The cathodes were investigated by electrochemical measurements, and surface and morphological analyses before and after different operation times in chlor-alkali cells. Electrode stability was investigated by life-time tests. The surface properties of gas diffusion electrodes were studied for both fresh and used cathodes by X-ray photoelectron spectroscopy (XPS). Transmission (TEM) and scanning electron microscopy (SEM-EDX) were used to investigate morphology. The bulk of gas diffusion electrodes was studied by X-ray diffraction (XRD) and thermogravimetric analysis (TG-DSC). At least two main degradation processes that occur on different time-scales were identified and attributed to segregation and loss of the second metal at the interface and a decrease in the hydrophilic properties with time. Furthermore, an increase in the precipitation of compounds from the reaction process also decreased performance by the occlusion of reaction pores.     

Bifunctional electrodes for unitised regenerative fuel cells

The effects of different configurations and compositions of platinum and iridium oxide electrodes for the oxygen reaction of unitised regenerative fuel cells (URFC) are reported. Bifunctional oxygen electrodes are important for URFC development because favourable properties for the fuel cell and the electrolysis modes must be combined into a single electrode. The bifunctional electrodes were studied under different combinations of catalyst mixtures, multilayer arrangements and segmented configurations with single catalyst areas. Distinct electrochemical behaviour was observed for both modes and can be explained on the basis of impedance spectroscopy. The mixture of both catalysts performs best for the present stage of electrode development. Also, the multilayer electrodes yielded good results with the potential for optimisation. The influence of ionic and electronic resistances on the relative performance is demonstrated. However, penalties due to cross currents in the heterogeneous electrodes were identified and explained by comparing the performance curves with electrodes composed of a single catalyst. Potential improvements for the different compositions are discussed.     

Effect of PTFE Content in Gas Diffusion Media and Microlayer on the Performance of PEMFC Tested under Ambient Pressure

Polytetrafluoroethylene (PTFE) content in the fuel cell electrode plays an important role on the performance of polymer electrolyte membrane fuel cell (PEMFC) when the cell is tested under low temperature and under ambient pressure. PTFE is added to the PEM fuel cell electrode to improve the mechanical strength and to help in removing the product water formed on the cathode; however, higher PTFE loading increases the resistance and thus decreases the performance of the cell and very low PTFE content has the disadvantage of water flooding in long‐term operation. We have investigated the effect of the PTFE content in the gas diffusion media (carbon paper) and in the microlayer on the performance of PEMFC operating at ambient pressure. The PTFE contents in these two layers have to be finely matched to get the best performance of the cells. The polarisation behaviour, electrochemical surface area and the electrochemical impedance spectra have been analysed. The results are presented in this paper.     

Shunt current protocol to eliminate reversible degradation of polymer electrolyte membrane fuel cells during constant load operations

The objective of this study is to determine the durability of polymer electrolyte membrane fuel cells (PEMFCs) in constant current operation incorporated with regular recovery protocol for eliminating reversible performance loss of membrane electrode assemblies. Effects of operation ‘shunt current protocol’ on PEMFC durability are studied through analyses of the main degradation mechanism based on results of electrochemical characterizations and post-mortem investigations. The voltage of the protected cell using the shunt current protocol is stably preserved under the applied current density for 700 h with less degradation (4.2% of decay ratio), while the performance of the unprotected cell steadily decreased with time (15.1% over 700 h). The substantial performance deterioration of the unprotected cell is mainly attributed to morphology deterioration of the cathode catalyst layer with oxidation of Pt catalysts and chemical degradation of ionomers caused by generation of excessive water from electrochemical oxygen reduction reactions under high-humidity operating conditions. In contrast, the shunt current protocol plays an important role in sustaining high oxygen activity at the cathode catalyst surface, detaching partially covered OH⁻ species on Pt active sites from water oxidation during cell operation caused by periodically applied shunt current for a very short period of 1 s every 5 h. We hope to provide insight into the operation protocol to extend the lifetime of PEMFCs, minimizing conversion from recoverable performance loss to irreversible (permanent) degradation during operation.     

Direct ethanol fuel cells with catalysed metal mesh anodes

Platinum based binary and ternary catalysts prepared by thermal decomposition on titanium mesh were characterised and compared in terms of the electrochemical activity for ethanol oxidation. An enhancement in the catalytic activity was observed for the binary catalyst containing tin and ruthenium in their compositions with platinum. The catalysts were tested in single direct ethanol fuel cells and the result obtained with PtRu and PtSn showed that the mesh based electrodes show competitive performance in comparison to the conventional carbon based anodes.     

Electrochemical synthesis of hydrogen peroxide: Rotating disk electrode and fuel cell studies

The electrochemical reduction of oxygen on various catalysts was studied using the thin-layer rotating disk electrode (RDE) method. High-surface-area carbon was modified with an anthraquinone derivative and gold nanoparticles. Polytetrafluoroethylene (PTFE) and cationic polyelectrolyte (FAA) were used as binders in the preparation of thin-film electrodes. Our primary goal was to find a good electrocatalyst for the two-electron reduction of oxygen to hydrogen peroxide. All electrochemical measurements were carried out in 0.1 M KOH. Cyclic voltammetry was used in order to characterise the surface processes of the modified electrodes in O₂-free electrolyte. The RDE results revealed that the carbon-supported gold nanoparticles are active catalysts for the four-electron reduction of oxygen in alkaline solution. Anthraquinone-modified high-area carbon catalyses the two-electron reduction at low overpotentials, which is advantageous for hydrogen peroxide production.In addition, the polymer electrolyte fuel cell technology was used for the generation of hydrogen peroxide. The cell was equipped with a bipolar membrane which consisted of commercial Nafion 117 as a cation-exchange layer and FT-FAA as an anion-exchange layer. The bipolar membranes were prepared by a hot pressing method. Use of the FAA ionomer as a binder for the anthraquinone-modified carbon catalyst resulted in production of hydrogen peroxide.     

Sub-freezing endurance of PEM fuel cells with different catalyst-coated membranes

The sub-freezing endurance of proton exchange membrane (PEM) fuel cells with hydrophobic and hydrophilic catalyst-coated membranes (CCMs) was investigated. The polarization curves, electrochemical characteristics and physical structures of the CCMs were measured. The cells were frozen at −20 °C with saturated residual water after operating at 60 °C. After eight freeze/thaw cycles, no evident negative effect on the performance of the cell with a hydrophobic CCM was observed, while the cell with a hydrophilic CCM degraded severely. By analyzing the polarization curves, it was concluded that the mass transport limitation was the main reason for the performance loss of the hydrophilic cell. The electrochemical active surface area (ECA) results suggest that the hydrophobicity of the catalyst layer (CL) has an apparent impact on the residual water distribution of the membrane electrode assembly (MEA). A larger water content in the hydrophilic CL has a negative effect on the subzero endurance. From the polarization resistance obtained from electrochemical impedance spectroscopy (EIS) the origin of degradation was further clarified. Mercury intrusion porosimetry showed that the pore size of the hydrophilic catalyst layer changed significantly after freezing; the mean pore size increased from 5.68 to 6.71 nm. However, with a water removal method, namely, gas purging, it was possible to prevent degradation effectively.     

Functionalized carbon support with sulfonated polymer for direct methanol fuel cells

Recently electrodes for direct methanol fuel cell (DMFC) have been developed for getting high fuel cell performances by controlling composition of catalysts and sulfonated polymers, developing catalyst particles, modifying carbon supports, etc. The electrodes in DMFCs are porous layers, which are composed of catalyst, which is black or carbon supported, and sulfonated polymers in a blended form. In the present study, carbon support for catalysts was functionalized to play dual roles of a mass transport and a catalyst support. The functionalized carbon support was characterized and compared with pristine one by thermal and spectroscopic analysis, and loading of platinum (Pt) catalysts on modified support was performed by gas reduction. The electrodes with Pt on functionalized carbon support were fabricated, though the conventional electrodes were prepared with sulfonated polymer and Pt catalysts. Membrane electrode assembly with Pt catalyst on functionalized support showed a higher DMFC performance of 30 mW cm⁻² at 50 °C without using additional sulfonated polymer. Integration of electrode components in one body has another advantage of easier and simpler process in preparing electrodes for DMFCs. Improved DMFC performance of the electrode containing functionalized carbon was be attributed to a better mass transport which maximize the catalytic activities.     

Systematic study of back pressure and anode stoichiometry effects on spatial PEMFC performance distribution

A segmented cell system was applied to investigate the effects of the anode and cathode back pressure and hydrogen stoichiometry on fuel cell performance in terms of overpotential distributions along the flow field. The segmented cell system was designed with closed loop Hall sensors and a data acquisition system allowing simultaneous spatial electrochemical impedance spectra (EIS) measurements. It was determined that an increase in back pressure for the tested serpentine flow field design results in an improvement of the cell performance and uneven improvement of individual segments’ performance. In general, the performance and the overpotentials become more uniform downstream with an increase in the back pressure due to a decrease in activation and mass transfer losses. Spatial EIS data for the PEMFC operated at different back pressures support the overpotential analysis. Hydrogen stoichiometry variations do not affect the performance of the cell or the individual segments at low current density because there is no significant hydrogen concentration gradient in the flow field. However, at high current densities a reduction in hydrogen stoichiometry produces a slight decrease in performance for inlet segments while outlet segments showed a noticeable performance loss. The decrease in performance is attributed to an increase in mass transfer losses due to nitrogen diffusion from the cathode to the anode. This effect becomes more pronounced for the outlet segments due to a downstream nitrogen accumulation. Under high current density conditions, the cell is locally fuel starved even with a high fuel stoichiometry creating conditions leading to cell degradation by carbon corrosion. More importantly, this local degradation is masked by the overall cell performance which remains largely unaffected.