Polymer electrolyte fuel cells (PEFC) convert chemicalenergy into electrical energy with higher efficiency thaninternal combustion engines. They are particularly suited fortransportation applications or portable devices owing to theirhigh power density and low operating temperature. The latter ishowever detrimental to the kinetics of electrochemicalreactions and in particular to the reduction of oxygen at thecathode. The latter reaction requires enhancing by the verybest catalyst, today platinum. Even so, the cathode isresponsible for the main loss of voltage in the cell. Moreover,the scarce and expensive nature of platinum craves theoptimisation of its use. The purpose of this thesis was to better understand thefunctioning of the porous cathode in the PEFC. This wasachieved by developing physical models to predict the responseof the cathode to steady-state polarisation, currentinterruption (CI) and electrochemical impedance spectroscopy(EIS), and by comparing these results to experimental ones. Themodels account for the kinetics of the oxygen reduction as wellas for the transport of the reactants throughout the cathode,i.e. diffusion of gases and proton migration. The agglomeratestructure was assumed for the description of the internalstructure of the cathode. The electrochemical experiments wereperformed on electrodes having a surface of 0.5 cm2 using alaboratory fuel cell. The response of the cathode to various electrodecompositions, thickness, oxygen pressure and relative humiditywas experimentally investigated with steady-state polarisation,EIS and CI techniques. It is shown that a content in thecathode of 35-43 wt % of Nafion, the polymer electrolyte, gavethe best performance. Such cathodes display a doubling of theapparent Tafel slope at high current density. In this region,the current is proportional to the cathode thickness and to theoxygen pressure, which, according to the agglomerate model,corresponds to limitation by oxygen diffusion in theagglomerates. The same analysis was made using EIS. Moreover,experimental results showed that the Tafel slope increases fordecreasing relative humidity. For Nafion contents lower than 35wt %, the cathode becomes limited by proton migration too. ForNafion contents larger than 40 wt %, the cathode performance athigh current density decreases again owing to an additionalmass transport. The latter is believed to be oxygen diffusionthroughout the cathode. The activity for oxygen reduction ofcatalysts based on iron acetate adsorbed on a carbon powder andpyrolysed at 900°C in ammonia atmosphere was alsoinvestigated. It was shown that the choice of carbon has atremendous effect. The best catalysts were, on a weight basis,as active as platinum. <b>Keywords:</b>polymer electrolyte fuel cell, cathode, masstransport, porous electrode, modelling, agglomerate model,electrochemical impedance spectroscopy, current interrupt,transient techniques, non-noble catalysts

Polymer electrolyte fuel cells (PEFC) convert the chemically bound energy in a fuel, e.g. hydrogen, directly into electricity by an electrochemical process. Examples of future applications are energy conversion such as combined heat and power generation (CHP), zero emission vehicles (ZEV) and consumer electronics. One of the key components in the PEFC is the membrane / electrode assembly (MEA). Both the membrane and the electrodes consist of proton conducting polymers (ionomers). In the membrane, properties such as gas permeability, high proton conductivity and sufficient mechanical and chemical stability are of crucial importance. In the electrodes, the morphology and electrochemical characteristics are strongly affected by the ionomer content. The primary purpose of the present thesis was to develop experimental techniques and to use them to characterise proton conducting polymers and membranes for PEFC applications electrochemically at, or close to, fuel cell operating conditions. The work presented ranges from polymer synthesis to electrochemical characterisation of the MEA performance. The use of a sulfonated dendritic polymer as the acidic component in proton conducting membranes was demonstrated. Proton conducting membranes were prepared by chemical cross-linking or in conjunction with a basic functionalised polymer, PSU-pyridine, to produce acid-base blend membranes. In order to study gas permeability a new in-situ method based on cylindrical microelectrodes was developed. An advantage of this method is that the measurements can be carried out at close to real fuel cell operating conditions, at elevated temperature and a wide range of relative humidities. The durability testing of membranes for use in a polymer electrolyte fuel cell (PEFC) has been studied in situ by a combination of galvanostatic steady-state and electrochemical impedance measurements (EIS). Long-term experiments have been compared to fast ex situ testing in 3 % H2O2 solution. For the direct assessment of membrane degradation, micro-Raman spectroscopy and determination of ion exchange capacity (IEC) have been used. PVDF-based membranes, radiation grafted with styrene and sulfonated, were used as model membranes. The influence of ionomer content on the structure and electrochemical characteristics of Nafion-based PEFC cathodes was also demonstrated. The electrodes were thoroughly investigated using various materials and electrochemical characterisation techniques. Electrodes having medium Nafion contents (35&lt;x&lt;45 wt %) showed the best performance. The mass-transport limitation was essentially due to O2 diffusion in the agglomerates. The performance of cathodes with low Nafion content (&lt;30 wt %) is limited by poor kinetics owing to incomplete wetting of platinum (Pt) by Nafion, by proton migration throughout the cathode as well as by O2 diffusion in the agglomerates. At large Nafion content (&gt;45 wt %), the cathode becomes limited by diffusion of O2 both in the agglomerates and throughout the cathode. Furthermore, models for the membrane coupled with kinetics for the hydrogen electrode, including water concentration dependence, were developed. The models were experimentally validated using a new reference electrode approach. The membrane, as well as the hydrogen anode and cathode characteristics, was studied experimentally using steady-state measurements, current interrupt and EIS. Data obtained with the experiments were in good agreement with the modelled results. / QC 20101014

Hydrogen and oxygen or air polymer electrolyte membrane fuel cell is one of the most promising electrical energy conversion devices for a sustainable future due to its high efficiency and zero emission. Membrane electrode assembly (MEA), in which electrochemical reactions occur, is stated to be the heart of the fuel cell. The aim of this study was to develop methods for preparation of MEA with alternative polymer electrolyte membranes and compare their performances with the conventional Nafion&reg / membrane. The alternative membranes were sulphonated polyether-etherketone (SPEEK), composite, blend with sulphonated polyethersulphone (SPES), and polybenzimidazole (PBI). Several powder type MEA preparation techniques were employed by using Nafion&reg / membrane. These were GDL Spraying, Membrane Spraying, and Decal methods. GDL Spraying and Decal were determined as the most efficient and proper MEA preparation methods. These methods were tried to improve further by changing catalyst loading, introducing pore forming agents, and treating membrane and GDL. The highest performance, which was 0.53 W/cm2, for Nafion&reg / membrane was obtained at 70 0C cell temperature. In comparison, it was about 0.68 W/cm2 for a commercial MEA at the same temperature. MEA prepared with SPEEK membrane resulted in lower performance. Moreover, it was found that SPEEK membrane was not suitable for high temperature operation. It was stable up to 80 0C under the cell operating conditions. However, with the blend of 10 wt% SPES to SPEEK, the operating temperature was raised up to 90 0C without any membrane deformation. The highest power outputs were 0.29 W/cm2 (at 70 0C) and 0.27 W/cm2 (at 80 0C) for SPEEK and SPEEK-PES blend membrane based MEAs. The highest temperature, which was 150 0C, was attained with PBI based MEA during fuel cell tests.

Current environmental and energy sustainability trends have instigated considerable interest in alternative energy technologies that exhibit reduced dependence on fossil fuels. The advantages of such a direction are two-fold: reduced greenhouse gas emissions (notably CO2) and improved energy sustainability. Fuel cells are recognized as a potential technology that achieves both of these goals. However, improvements to fuel cell power density and stability must be realized to make them economically competitive with traditional, fossil-based technologies. The work in this dissertation is largely focused on the use of analytical tools for the study of transport processes in three fuel cell systems toward improvement of fuel cell performance. Polymer electrolyte membrane fuel cells (PEMFCs) are fueled by hydrogen and oxygen to generate electrical current. Microbial fuel cells (MFCs) use bacteria to degrade carbon compounds, such as those found in wastewaters, and simultaneously generate an electric current. Enzyme fuel cells (EFCs) operate similarly to PEMFCs but replace precious metal catalysts, such as platinum, with biologically-derived enzymes. The use of enzymes also allows EFCs to utilize simple carbon compounds as fuel. The operation of all three fuel cell systems involves different modes of ion and electron transport and can be affected negatively by transport limitations. Electrochemical impedance spectroscopy (EIS) was used in this work to study the distribution of transport resistances in all three fuel cell systems. The results of EIS were used to better understand the transport resistances that limited fuel cell power output. By using this technique, experimental conditions (including operating conditions, construction, and materials) were identified to develop fuel cells with greater power output and longevity. In addition to EIS, neutron imaging was employed to quantify the distribution of water in PEMFCs and EFCs. Water content is an integral aspect of providing optimal power output from both fuel cell systems. Neutron imaging contributed to developing an explanation for the loss of water observed in an operating EFC despite conditions designed to mitigate water loss. The findings of this dissertation contribute to the improvement of fuel cell technology in an effort to make these energy devices more economically viable.

A fuel cell is an electrochemical power source with advantages of both the combustion engine and the battery. Like a combustion engine, a fuel cell will run as long as it is provided fuel; and like a battery, fuel cells convert chemical energy directly to electrical energy. As an electrochemical power source, fuel cells are not subjected to the Carnot limitations of combustion (heat) engines. Fuel cells bear similarity to batteries, with which they share the electrochemical nature of the power generation process and to the engines that, unlike batteries, will work continuously consuming a fuel of some sort. A fuel cell operates quietly and efficiently and, when hydrogen is used as a fuel, it generates only power and water. Thus, a fuel cell is a so called ‘zero-emission engine’. In the past, several fuel cell concepts have been tested in the laboratory but the systems that are being potentially considered for commercial developments are: (i) Alkaline Fuel Cells (AFCs), (ii) Phosphoric Acid Fuel Cells (PAFCs), (iii) Polymer Electrolyte Fuel Cells (PEFCs), (iv) Solid Polymer Electrolyte Direct Methanol Fuel Cells (SPE-DMFCs), (v) Molten Carbonate Fuel Cells (MCFCs) and (vi) Solid Oxide Fuel Cells (SOFCs). Among the aforesaid systems, PEFCs that employ hydrogen as fuel are considered attractive power systems for quick start-up and ambient temperature operations. Ironically, however, hydrogen as fuel is not available freely in the nature. Accordingly, it has to be generated from a readily available hydrogen carrying fuel such as natural gas, which needs to be reformed. But, such a process leads to generation of hydrogen contaminated with carbon monoxide, which even at minuscule level is detrimental to the fuel cell performance. Pure hydrogen can be generated through water electrolysis but hydrogen thus generated needs to be stored as compressed/liquefied gas, which is cost-intensive. Therefore, certain hydrogen carrying organic fuels such as methanol, ethanol, propanol, ethylene glycol and diethyl ether have been considered for fueling PEFCs directly. Among these, methanol with hydrogen content of about 12.8 wt.% (specific energy = 6.1kWh kg-1) is the most attractive organic liquid. PEFCs using methanol directly as fuel are referred to as SPE-DMFCs. But SPE-DMFCs suffer from methanol crossover across the polymer electrolyte membrane, which affects the cathode performance and hence the fuel cell during its operation. SPE-DMFCs also have inherent limitations of low open-circuit-potential and low electrochemical-activity. An obvious solution to the aforesaid problems is to explore other promising hydrogen carrying fuels such as sodium borohydride (specific energy = 12kWh kg-1), which has a capacity value of 5.67Ah g-1 and a hydrogen content of about 11wt.%. Such fuel cells are called direct borohydride fuel cells (DBFCs). This thesis is directed to studies on SPE-DMFCs and DBFCs

<p>Polymer electrolyte fuel cells (PEFC) convert chemicalenergy into electrical energy with higher efficiency thaninternal combustion engines. They are particularly suited fortransportation applications or portable devices owing to theirhigh power density and low operating temperature. The latter ishowever detrimental to the kinetics of electrochemicalreactions and in particular to the reduction of oxygen at thecathode. The latter reaction requires enhancing by the verybest catalyst, today platinum. Even so, the cathode isresponsible for the main loss of voltage in the cell. Moreover,the scarce and expensive nature of platinum craves theoptimisation of its use.</p><p>The purpose of this thesis was to better understand thefunctioning of the porous cathode in the PEFC. This wasachieved by developing physical models to predict the responseof the cathode to steady-state polarisation, currentinterruption (CI) and electrochemical impedance spectroscopy(EIS), and by comparing these results to experimental ones. Themodels account for the kinetics of the oxygen reduction as wellas for the transport of the reactants throughout the cathode,i.e. diffusion of gases and proton migration. The agglomeratestructure was assumed for the description of the internalstructure of the cathode. The electrochemical experiments wereperformed on electrodes having a surface of 0.5 cm2 using alaboratory fuel cell.</p><p>The response of the cathode to various electrodecompositions, thickness, oxygen pressure and relative humiditywas experimentally investigated with steady-state polarisation,EIS and CI techniques. It is shown that a content in thecathode of 35-43 wt % of Nafion, the polymer electrolyte, gavethe best performance. Such cathodes display a doubling of theapparent Tafel slope at high current density. In this region,the current is proportional to the cathode thickness and to theoxygen pressure, which, according to the agglomerate model,corresponds to limitation by oxygen diffusion in theagglomerates. The same analysis was made using EIS. Moreover,experimental results showed that the Tafel slope increases fordecreasing relative humidity. For Nafion contents lower than 35wt %, the cathode becomes limited by proton migration too. ForNafion contents larger than 40 wt %, the cathode performance athigh current density decreases again owing to an additionalmass transport. The latter is believed to be oxygen diffusionthroughout the cathode. The activity for oxygen reduction ofcatalysts based on iron acetate adsorbed on a carbon powder andpyrolysed at 900°C in ammonia atmosphere was alsoinvestigated. It was shown that the choice of carbon has atremendous effect. The best catalysts were, on a weight basis,as active as platinum.</p><p><b>Keywords:</b>polymer electrolyte fuel cell, cathode, masstransport, porous electrode, modelling, agglomerate model,electrochemical impedance spectroscopy, current interrupt,transient techniques, non-noble catalysts</p>

<p>The objectives of this doctoral thesis are to give a basisincluding methods for the development of stationary polymerelectrolyte fuel cell (PEFC) systems for combined heat andpower production. Moreover, the objectives include identifyingprerequisites, requirements and possibilities for PEFC systemsproducing heat and power for buildings in Sweden. The PEFCsystem is still in a pre-commercial state, but low emissionlevels, fast dynamics and high efficiencies are promisingcharacteristics.</p><p>A thermodynamic model to simulate stationary PEFC systemshas been constructed and pinch technology and exergy analysesare utilised to design and evaluate the system. The finalsystem configuration implies a high total efficiency ofapproximately 98 % (LHV).</p><p>A flexible test facility was built in connection with theresearch project to experimentally evaluate small-scalestationary PEFC systems at KTH. The research PEFC system hasextensive measurement equipment, a rigorous control system andallows fuel cell systems from approximately 0.2 to 4 kWel insize to be tested. The simulation models of the fuel processorand the fuel cell stack are verified with experimental datataken from the test facility. The initial evaluation andsimulation of the first residential installation of a PEFCsystem in Sweden is also reported. This PEFC system, fuelled bybiogas and hydrogen, is installed in an energy system alsoincluding a photovoltaic array, an electrolyser and hydrogenstorage.</p><p>Technical aspects of designing a fuel cell system-basedenergy system, including storages and grid connections, whichprovides heat and power to a building are presented in thisthesis. As a basis for the technical and economic evaluations,exemplifying energy systems are constructed and simulated. Fuelcell system installations are predicted to be economicallyunviable for probable near-term conditions in Sweden. The mainfactor in the economic evaluations is the fuel price. However,fuel cell system installations are shown to have a higher fuelutilisation than the conventional method of energy supply.</p><p>The methods presented in this thesis serve as a collectedbasis for continued research and development in the area.</p><p><b>Keywords:</b>Small-scale, stationary, fuel cell system,polymer electrolyte fuel cell, PEFC system, reformer,thermodynamic modelling, pinch technology, exergy analyses,system configuration, test facility, experiments, application,simulation, installation, energy system, energy storage, heatand power demand.</p>

<p>Polymer electrolyte fuel cells (PEFC) convert the chemically bound energy in a fuel, e.g. hydrogen, directly into electricity by an electrochemical process. Examples of future applications are energy conversion such as combined heat and power generation (CHP), zero emission vehicles (ZEV) and consumer electronics. One of the key components in the PEFC is the membrane / electrode assembly (MEA). Both the membrane and the electrodes consist of proton conducting polymers (ionomers). In the membrane, properties such as gas permeability, high proton conductivity and sufficient mechanical and chemical stability are of crucial importance. In the electrodes, the morphology and electrochemical characteristics are strongly affected by the ionomer content. The primary purpose of the present thesis was to develop experimental techniques and to use them to characterise proton conducting polymers and membranes for PEFC applications electrochemically at, or close to, fuel cell operating conditions. The work presented ranges from polymer synthesis to electrochemical characterisation of the MEA performance.</p><p>The use of a sulfonated dendritic polymer as the acidic component in proton conducting membranes was demonstrated. Proton conducting membranes were prepared by chemical cross-linking or in conjunction with a basic functionalised polymer, PSU-pyridine, to produce acid-base blend membranes. In order to study gas permeability a new in-situ method based on cylindrical microelectrodes was developed. An advantage of this method is that the measurements can be carried out at close to real fuel cell operating conditions, at elevated temperature and a wide range of relative humidities. The durability testing of membranes for use in a polymer electrolyte fuel cell (PEFC) has been studied in situ by a combination of galvanostatic steady-state and electrochemical impedance measurements (EIS). Long-term experiments have been compared to fast ex situ testing in 3 % H2O2 solution. For the direct assessment of membrane degradation, micro-Raman spectroscopy and determination of ion exchange capacity (IEC) have been used. PVDF-based membranes, radiation grafted with styrene and sulfonated, were used as model membranes. The influence of ionomer content on the structure and electrochemical characteristics of Nafion-based PEFC cathodes was also demonstrated. The electrodes were thoroughly investigated using various materials and electrochemical characterisation techniques. Electrodes having medium Nafion contents (35<x<45 wt %) showed the best performance. The mass-transport limitation was essentially due to O2 diffusion in the agglomerates. The performance of cathodes with low Nafion content (<30 wt %) is limited by poor kinetics owing to incomplete wetting of platinum (Pt) by Nafion, by proton migration throughout the cathode as well as by O2 diffusion in the agglomerates. At large Nafion content (>45 wt %), the cathode becomes limited by diffusion of O2 both in the agglomerates and throughout the cathode. Furthermore, models for the membrane coupled with kinetics for the hydrogen electrode, including water concentration dependence, were developed. The models were experimentally validated using a new reference electrode approach. The membrane, as well as the hydrogen anode and cathode characteristics, was studied experimentally using steady-state measurements, current interrupt and EIS. Data obtained with the experiments were in good agreement with the modelled results. Keywords: polymer electrolyte fuel cell, proton conducting membrane, porous electrode, gas permeability, degradation, water transport</p>

<p>In this study novel composite electrodes were developed, in which the catalytic components were deposited in nanoparticulate form. The efficiency of the nanophase catalysts and membrane electrodes were tested in an important electrocatalytic process, namely hydrogen production by water electrolysis, for renewable energy systems. The activity of electrocatalytic nanostructured electrodes for hydrogen production by water electrolysis were compared with that of more conventional electrodes. Development of the methodology of preparing nanophase materials in a rapid, efficient and simple manner was investigated for potential application at industrial scale. Comparisons with industry standards were performed and electrodes with incorporated nanophases were characterized and evaluated for activity and durability.</p>

De nouvelles familles de liquides ioniques conducteurs par ion lithium; à anions aromatiques et aliphatiques de type perfluorosulfonate perfluorosulfonylimidure attachés à des oligoéthers (méthoxy polyéthylène glycol mPEG) de longueurs différentes ont été synthétisées et caractérisées dans le but d'améliorer l'interaction entre les chaînes de POE et les sels de lithium en améliorant la mobilité segmentaire. Ainsi différentes membranes amorphes ou peu cristallines améliorent le transport cationique par rapport aux électrolytes polymères usuels. . Leurs propriétés ont été évaluées dans deux types de polymères hôtes : un polyéther linéaire (POE) et un polyéther réticulé préparé par un procédé "VERT". Leurs parties oligooxyéthylène aident à la solvatation des cations lithium et conduisent à l'augmentation des propriétés de transport; c'est à dire la conductivité cationique et le nombre de transport. Leurs stabilités thermiques et électrochimiques sont adaptées à l'application batterie lithium-polymère. / The new families of lithium-conducting ionic liquids; aromatic and aliphatic lithium salts based on perfluorosulfonate and perfluorosulfonylimide anions attached to an oligoether (methoxy polyethylene glycol mPEG) with different lengths were synthesized and characterized with the aim to improve the salt interaction with the host polymer's POE chains while keeping a high segmental mobility. They allowed obtaining membranes with lower crystallization degree and higher cationic transport number as compared with benchmarked salts. Their properties as lithium salts were investigated in two types of host polymers i.e. a linear polyether (POE) and a cross-linked polyether prepared by a ‘GREEN' process. Their oligooxyethylene moieties improve the lithium cation solvation leading to an increase in cationic transference numbers. Their electrochemical and thermal stabilities are suitable for lithium battery application.