Proton exchange membrane (PEM) fuel cell technology is promissing alternative solution to today&rsquo / s energy concerns providing clean environment and efficient system. Decreasing platinum (Pt) content of fuel cell is one of the main goals to reduce high costs of fuel cell technology in the way of commercialization. In this target, porous carbons provide an alternative solution as a support material for fuel cell electrocatalysts. It is also essential to increase surface area of carbon support material to have well dispersion of the Pt nanoparticles. The aim of this thesis is to synthesize mesoporous carbon supports named as hollow core mesoporous shell (HCMS) carbon and prepare their corresponding electrocatalysts with platinum impregnation method. HCMS carbon supports were synthesized by using two different carbon sources. As a first approach, phenol/paraformaldehyde couples were used and carbon source exhibited 1053 m 2 /g BET surface area and 1.046 nm BJH adsorption pore diameter. Second approach was to use divinylbenzene (DVB) as a carbon source with an initiator named as azo bis isobuytronitrile (AIBN) differing synthesis criteria. It is observed that using AIBN/DVB, pore sizes increased up to 3.44 nm. Platinum impregnation was conducted by microwave irradiation method using hydrogen hexachloroplatinate (IV) hydrate as a platinum precursor. The first achievement was to increase platinum loading up to 44 wt % on commercial Vulcan XC 72 by using ethylene glycol as a reducing agent. Using different reducing agents such as hydrazine, sodium borohydrate with a combination of ethylene glycol, platinum loading reached up to 34 wt % on HCMS carbon support. Accordingly, 34 wt %, 32 wt % and 28 wt % Pt/HCMS carbon supported electrodes preparation was achieved. The sizes of the platinum nanoparticles were calculated by XRD analysis as 4 nm, 4.2 nm and 4.5 nm for 28 wt %, 32 wt % and 34 wt % Pt/HCMS carbon supported electrodes respectively. Characterizations of catalysts were performed by ex situ (N 2 adsorption, TGA, SEM, TEM and Cyclic Voltammetry) and in situ (PEMFC tests) analysis.

Afin de rendre les piles à combustible à membrane échangeuse de protons viables économiquement dans le domaine automobile, des problèmes de durabilité et de coût sont à résoudre. La compréhension et le contrôle des dégradations à l'intérieur de la cellule et surtout de l'AME sont toujours le centre d’intérêt de nombreux laboratoires mais aussi d'industriels. Les milliers d'arrêt-démarrages subis par la pile provoquent une importante corrosion du support carbone. Le platine utilisé étant un catalyseur onéreux, la modélisation numérique permet l'analyse de phénomènes à moindre coût.Dans ces travaux, deux modèles ont été développés afin de modéliser les phases transitoires que sont les arrêt-démarrages. Tout d'abord, une étude sur les performances de la pile a été effectuée en utilisant le modèle. Le couplage entre les modèles le long du canal et dent/canal est introduit. Ensuite, une analyse des phénomènes se déroulant durant les arrêt-démarrages est effectuée. Des phases temporelles sont proposées afin de découper ces différents phénomènes. Le mécanisme des courants inverses (durant lequel la corrosion du carbone apparaît) est minutieusement détaillé avec l'aide du modèle. L'accent est porté sur les hétérogéneités de dégradations apparaissant entre l'entrée et la sortie mais aussi entre le canal et la dent. Enfin, le modèle est utilisé afin de simuler et proposer des stratégies de mitigations. Les tendances attendues par la littérature sont confirmées mais aussi évaluées. Parmi les idées suggerées, l'optimisation du design dent/canal tout au long du canal est proposée afin de limiter les dégradations. / In order to make Proton Exchange Membrane Fuel Cells economically viable for an automotive application, durability and cost problems have to be addressed. Understanding and mitigating degradations inside the cell especially in the MEA are still the focus of several laboratories and also industrials. The several thousands startups and shutdowns that the fuel cell underwent induce severe corrosion of the carbon support. As the catalyst used is expensive, namely platinum, modeling is a great asset to comprehend and analyze this phenomenon costwise.In this work, two models were developed for modeling the transient phases that are the startup and shutdown. First a performance study is presented to validate the use of the model and to introduce the coupling between the along the channel model and the rib/channel model. Then an analysis of the phenomena occurring during the startup (and shutdown) is carried out. Phases are suggested to break down the different phenomena. The reverse-current decay mechanism, when carbon corrosion occurs, is thoroughly detailed using the model. Degradation heterogeneities are highlighted whether they are between inlet and outlet or rib and channel. Finally the model is used to emulate and suggest mitigation strategies. Degradation trends are confirmed and evaluated. New ideas like an original flow field design are tested to mitigate degradation.

The polymer electrolyte fuel cell converts the chemical energy in a fuel, e.g. hydrogen or methanol, and oxygen into electrical energy. The high efficiency and the possibility to use fuel from renewable sources make them attractive as energy converters in future sustainable energy systems. Great progress has been made in the development of the PEFC during the last decade, but still improved lifetime as well as lowered cost is needed before a broad commercialization can be considered. The electrodes play an important role in this since the cost of platinum used as catalyst constitutes a large part of the total cost for the fuel cell. A large part of the degradation in performance can also be related to the degradation of the porous electrode and a decreased electrochemically active Pt surface. In this thesis, different fuel cell reactions, catalysts and support materials are investigated with the aim to investigate the possibility to improve the activity, stability and utilisation of platinum in the fuel cell electrodes. An exchange current density, i0, of 770 mA cm-2Pt was determined for the hydrogen oxidation reaction in the fuel cell with the model electrodes. This is higher than previously found in literature and implies that the kinetic losses on the anode are very small. The anode loading could therefore be reduced without imposing too high potential losses if good mass transport of hydrogen is ensured. It was also shown that the electrochemically active surface area, activity and stability of the electrode can be affected by the support material. An increased activity was observed at higher potentials for Pt deposited on tungsten oxide, which was related to the postponed oxide formation for Pt on WOx. An improved stability was seen for Pt deposited on tungsten oxide and on iridium oxide. A better Pt stability was also observed for Pt on a low surface non-graphitised support compared to a high surface graphitised support. Pt deposited on titanium and tungsten oxide, displayed an enhanced electrochemically active surface area in the cyclic voltammograms, which was explained by the good proton conductivity of the metal oxides. CO-stripping was shown to provide the most reliable measure of the electrochemically active surface area of the electrode in the fuel cell. It was also shown to be a useful tool in characterization of the degradation of the electrodes. In the study of oxidation of small organic compounds, the reaction was shown to be affected by the off transport of reactants and by the addition of chloride impurities. Pt and PtRu were affected differently, which enabled extraction of information about the reaction mechanisms and rate determining steps. The polymer electrolyte fuel cell converts the chemical energy in a fuel, e.g. hydrogen or methanol, and oxygen into electrical energy. The high efficiency and the possibility to use fuel from renewable sources make them attractive as energy converters in future sustainable energy systems. Great progress has been made in the development of the PEFC during the last decade, but still improved lifetime as well as lowered cost is needed before a broad commercialization can be considered. The electrodes play an important role in this since the cost of platinum used as catalyst constitutes a large part of the total cost for the fuel cell. A large part of the degradation in performance can also be related to the degradation of the porous electrode and a decreased electrochemically active Pt surface. In this thesis, different fuel cell reactions, catalysts and support materials are investigated with the aim to investigate the possibility to improve the activity, stability and utilisation of platinum in the fuel cell electrodes. An exchange current density, i0, of 770 mA cm-2Pt was determined for the hydrogen oxidation reaction in the fuel cell with the model electrodes. This is higher than previously found in literature and implies that the kinetic losses on the anode are very small. The anode loading could therefore be reduced without imposing too high potential losses if good mass transport of hydrogen is ensured. It was also shown that the electrochemically active surface area, activity and stability of the electrode can be affected by the support material. An increased activity was observed at higher potentials for Pt deposited on tungsten oxide, which was related to the postponed oxide formation for Pt on WOx. An improved stability was seen for Pt deposited on tungsten oxide and on iridium oxide. A better Pt stability was also observed for Pt on a low surface non-graphitised support compared to a high surface graphitised support. Pt deposited on titanium and tungsten oxide, displayed an enhanced electrochemically active surface area in the cyclic voltammograms, which was explained by the good proton conductivity of the metal oxides. CO-stripping was shown to provide the most reliable measure of the electrochemically active surface area of the electrode in the fuel cell. It was also shown to be a useful tool in characterization of the degradation of the electrodes. In the study of oxidation of small organic compounds, the reaction was shown to be affected by the off transport of reactants and by the addition of chloride impurities. Pt and PtRu were affected differently, which enabled extraction of information about the reaction mechanisms and rate determining steps. / Polymerelektrolytbränslecellen omvandlar den kemiska energin i ett bränsle, exv. vätgas eller metanol, och syrgas  till elektrisk energi. Den höga verkningsgraden samt möjligheten att använda bränsle från förnyelsebara källor gör dem attraktiva som energiomvandlare i framtida hållbara energisystem. En enorm utveckling har skett under det senaste årtiondet men för att kunna introducera polymerelektrolytbränslecellen på marknaden i en större skala måste livstiden öka och kostnaden minska. Elektroderna har en central del i detta då den platina som används som katalysator står för en stor del av kostnaden för bränslecellen. En stor del av prestandaförsämringen med tiden hos bränslecellen kan också relateras till en degradering av den porösa elektroden och en minskad elektrokemiskt aktiv platinayta. I denna avhandling studeras olika bränslecellsreaktioner samt olika katalysatorer och supportmaterial med målet att undersöka möjligheten att förbättra platinakatalysatorns aktivitet, stabilitet och utnyttjandegrad i bränslecellselektroder. Utbytesströmtätheten, i0, för vätgasoxidationen i bränslecell bestämdes till 770 mA cm-2Pt genom försök med modellelektroderna. Denna var högre än vad som framkommit tidigare i litteratur, vilket visar att de kinetiska förlusterna på anoden är mycket små. Katalysatormängden på anoden borde därför kunna minskas utan några större potentialförluster så länge masstransporten av vätgas är tillräcklig. Den elektrokemiskt aktiva ytan, aktiviteten och stabiliteten hos elektroden visade sig kunna påverkas av supportmaterialet. Platina deponerad på volfram oxid hade en högre aktivitet vid höga potentialer vilket relaterades till den förskjutna oxidbildningen på ytan. Elektroder med platina på volframoxid och iridiumoxid var mer stabila än elektroder med platina på kol. Det var även platina på ett icke grafitiserat kol med låg yta jämfört med platina på grafitiserade kol med en hög yta. Platina på metalloxidskikt av volfram och titan visade en högre elektrokemiskt aktiv yta i de cykliska voltamogrammen än platina på kol, vilket förklarades med att båda metalloxiderna har en bra protonledningsförmåga. CO-stripping gav det säkraste måttet på den elektrokemiskt aktiva ytan i en elektrod i bränslecell. CO-stripping visade sig även vara användbart för karaktärisering av degraderingen av en elektrod. Oxidationen av små organiska föreningar påverkades av borttransporten av intermediärer samt av kloridföroreningar. Pt aoch PtRu påverkades olika vilket gjorde det möjligt att få fram information om reaktionsmekanismer och hastighetsbestämmande steg. / QC 20101014