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Sjöfarten står för 3 % av världens totala växthusgaser och är idag högst beroende av fossila bränslen. Ett alternativ för att gå över till en fossilfri flotta är användning av bränsleceller och vätgas som drivmedel. Om vätgasen produceras från elektrolys med förnyelsebara energikällor så är driften utsläppsfri och koldioxidneutral. Bränsleceller kan användas i många olika sammanhang, men har ännu inte slagit igenom med full kraft. En anledning till detta är livslängden som är för kort. För att sjöfarten ska kunna implementera bränslecellsdrift behöver nedbrytningen av bränslecellen bli vidare utforskad och motverkad. Syftet med detta examensarbete var att hitta de mest signifikanta nedbrytningsmekanismerna för sjöfarten samt att bygga en modell för att förutspå livslängden utifrån lastprofiler från fartyg.  Rapportens avgränsningar var att enbart studera PEM-bränsleceller tack vare dess höga energitäthet och att teknologin är närmast marknaden för mobila applikationer. En litteraturstudie genomfördes för att fastställa de viktigaste nedbrytningsmekanismerna samt de faktorer som begränsar livslängden. Dessa bestämdes till start/stop cykler samt lastcykler vilka försämrar konduktiviteten i membranet samt minskar den elektrokemiska ytarean. En empirisk modell från experiment från litteraturen etablerades för att hitta relationen mellan parametrarna konduktivitet och elektrokemisk ytarea som funktion av start/stop cykler respektive lastcykler. En Comsol-modell användes för att utvärdera bränslecellens prestanda med dessa försämrade parametrar. Två lastprofiler analyserades och tolkades som antal start/stop cykler samt lastcykler för att utvärdera prestandan som funktion av antal år i drift. Båda fallen var i drift till dess att prestandan minskat med 20 % utvärderat vid strömtätheten 0.6 A/cm2. Båda lastprofilerna var utvärdera med olika körstrategier för att jämföra den modellerade livslängden beroende på ingångsvärden. Den första lastprofilen delades in i Case 1a och Case 1b där antalet start/stop cykler och lastcykler varierade. Resultatet visade att antalet timmar i drift mer än tredubblades i Case 1b där båda ingående indata hade minskats.   Case 2 delades upp i tre olika körstrategier där Case 2a var en referens som jämfördes mot Case 2b respektive Case 2c. Skillnaden mot Case 2b var att antalet start/stop cykler per dag multiplicerades med faktor 4. Resultatet från modellen var att livstiden minskade från 6 till 4 år. Vidare utvärderades Case 2c där istället antalet lastcykler dividerades med faktor 4, allt annat identiskt med Case 2a. Utfallet var en ökad livslängd från 6 år till 11 år, med totalt 32 032 timmar i drift. Denna livslängd kan jämföras med kommersialiserade marina produkter från Ballard och Powercell, där livslängden är 30 000 respektive 20 000 timmar i drift.  Sammanfattningsvis kan det konstateras att både start/stop cykler och lastcykler bryter ner bränslecellen och därmed minskar dess prestanda. Lastcykler var den faktor som var mest förödande gällande livslängden. Den modellerade livslängden på 32 032 timmar indikerar att den empirisk modellen tillsammans med Comsol-modellen genererade realistiska resultat. Slutligen kan sägas att ett område för framtida forskning inom ämnet innefattar lastcykler eftersom denna hade störst påverkan på modellen. Att särskilja olika typer av lastcykler och koppla till olika degradering skulle skapa än mer förståelse för livslängden. Då denna studie genomfördes på bränslecellsnivå skulle framtida studier kunna inkludera att analysera degradering på systemnivå för att få mer insikt i dessa processer. / The shipping industry emits 3 % of the global GHG-emissions and is highly dependent on fossil fuels. One alternative to decarbonise the sector is by utilising hydrogen in fuel cells. The propulsion is free from emissions if hydrogen is produced from renewables. The fuel cell technology can be applied in various applications but have not been fully commercialised. One of the biggest bottlenecks for fuel cell technology is the durability that needs to be improved. In order for marine vessels to implement hydrogen propulsion, the degradation need to be further understood and mitigated. The purpose of this thesis was to assess the most significant degradation mechanisms for marine applications and to build a model to evaluate the lifetime depending on load profiles. The scope of the thesis was to include PEMFCs since they have the highest power density and are closest to commercialisation for transport applications. A literature review was conducted to assess the most important degradation mechanisms and operating conditions that limits the lifetime, which concluded in start/stop cycling and load cycling. These conditions deteriorate the membrane conductivity and the electrochemical surface area. An empirical model based on experimental data from the literature was conducted to find relationships for conductivity and ECSA as function of start/stop cycling and load cycling, respectively. A Comsol model was established to evaluate performance reduction with degraded parameters. Two different load cycles were interpreted as number of start/stop cycles and load cycles in order to simulate the degradation. The output was polarization curves as function of operating years. Each case was operated until a performance reduction of 20 % was obtained at the current density of 0.6 A/cm2.  Both load profiles were analysed with different operation strategies to compare the resulting lifetime. The first load curve was divided into Case 1a and Case 1b where start/stop cycles and load cycles were altered. The results showed that the lifetime in operation hours was more than three-folded in Case 1b when the number of start/stop cycles and load cycles was reduced.  Case 2 was divided into three operating strategies. For comparison with Case 2a, the number of start/stop cycles per day in Case 2b was increased by a factor of 4. The result was that the lifetime declined from 6 to 4 years. Furthermore, Case 2c evaluated the lifetime if the number of load cycles per day decreased by a factor of 4, all else being equal to Case 2a. The outcome was an increment in lifetime from 6 to 11 years, with a total of 32 032 hours of operation. This lifetime can be compared to commercialised products from Ballard and Powercell with lifetimes of 30 000 and 20 000 operating hours, respectively. Conclusively, the simulations showed that both start/stop cycling and load cycling deteriorates the fuel cell performance. Load cycling is the operating condition that cause the most severe degradation. Moreover, the modelled lifetime of 32 032 hours indicates that the empirical model in combination with the Comsol model generate realistic lifetimes. Finally, since load cycling had the most vital impact on the lifetime, one of the topics for future research would be to distinguish different types of load cycles and connect to separate degradation outcomes. Since the model was on fuel cell level, future work could also include systems effects such as ripple current or distributions within fuel cell stacks.

Sjöfarten är idag dominerad av förbränningsmotorer som är beroende av fossila drivmedel. Elektrifiering är en av huvudstrategierna för att möjliggöra fossilfri energiförsörjning inom internationell sjöfart. Polymerelektrolytbränslecellen (PEMFC) omvandlar vätgas till elektricitet med hög verkningsgrad och är för närvarande kommersiellt tillgängligt upp till MW-skala för ett fartyg. Vätgas är en utmärkt energibärare för att tillgodose hög energidensitet hos ett fraktfartyg. Rippelströmmar från elkraftskomponenter påstås accelerera åldring av materialen i PEMFC och kan därför skapa negativa effekter över tid som påverkar livslängden av systemet.  De tillgängliga studier som utvärderar rippelströmmars påverkan på åldring i PEMFC är begränsade. Resultaten i dessa studier är tvetydiga och saknar tydliga kopplingar mellan rippelströmmarnas inverkan på åldringsfenomen, som på sikt kan påverka den tekniska livslängden. Målet med examensarbetet var att identifiera effekten av rippelströmmar på åldring av bränslecellen vid typiska körförhållanden för ett fraktfartyg. Tester genomfördes på en PEMFC genom att applicera en sinusformad (70 Hz, 50 % amplitud) rippelström på en dynamisk last som simulerar ett fraktfartyg. En konstant lastcykling vid 0.4 A/cm2 utfördes som ett komplement för att verifiera den dynamiska lastens inverkan på bränslecellen.  Alla tester resulterade i prestandaförluster både under den konstanta och dynamiska lasten, med eller utan rippelström. Men resultaten indikerade att effekten av en sinusformad rippelström inte orsakade någon signifikant åldring varken vid konstant respektive dynamisk lastcykel. / The marine shipping industry is dominated by fossil fuel driven propulsion. Electrification of marine vessels is one of the main strategies to enable emission-free propulsion. Hydrogen is an excellent energy carrier to meet the power demand of a marine vessel. Proton exchange membrane fuel cells (PEMFC) is a commercially available alternative for converting hydrogen into electricity. However, durability issues of the PEMFC is a constraint with the technology which limits technical lifetime. Research around ripple currents impact on degradation of PEMFC is scarce and the reported results are ambiguous and lack clear correlation between the effects of the ripple current on the lifetime of a PEMFC. This master thesis evaluates the impact on degradation of a single cell PEMFC by imposing a sinusoidal (70 Hz, 50 % amplitude) AC ripple to a dynamic load cycle. The dynamic load cycle is designed to simulate typical operating conditions of a marine vessel. Constant load cycling at 0.4 A/cm2 with the same ripple characteristics was also conducted to verify the dynamic load cycling impact on the performance losses of the PEMFC. The in-situ characterization showed performance losses both during the dynamic and constant load cycling, for the ripple current and reference tests. To conclude, no significant effects on degradation by the sinusoidal ripple current of 70 Hz and 50% amplitude is found when applied to a single cell PEMFC despite of performance losses for all cases.

In this dissertation, the effect of temperature and humidity on the viscoelastic and fracture properties of proton exchange membranes (PEM) used in fuel cell applications was studied. Understanding and accurately modeling the linear and nonlinear viscoelastic constitutive properties of a PEM are important for making hygrothermal stress predictions in the cyclic temperature and humidity environment of operating fuel cells. In this study, Nafion® NRE 211, Gore-Select® 57, and Ion Power® N111-IP were characterized under various humidity and temperature conditions. These membranes were subjected to a nominal strain in a dynamic mechanical analyzer (DMA), and their stress relaxation behavior was characterized over a period of time. Hygral master curves were constructed noting hygral shift factors, followed by thermal shifts to construct a hygrothermal master curve. This process was reversed (thermal shifts followed by hygral shifts) and was seen to yield a similar hygrothermal master curve. Longer term stress relaxation tests were conducted to validate the hygrothermal master curve. The Prony series coefficients determined based on the hygrothermal stress relaxation master curves were utilized in a linear viscoelastic stress model. The nonlinear viscoelastic behavior of the membranes was characterized by conducting creep tests on uniaxial tensile specimens at various constant stress conditions and evaluating the resulting isochronal stress-strain plots. The nonlinearity was found to be induced at relatively moderate stress/strain levels under dry conditions. To capture the nonlinearity, the well known Schapery model was used. To calculate the nonlinear parameters defined in the Schapery model, creep/recovery tests at various stress levels and temperatures were performed. A one-dimensional Schapery model was developed and then validated using various experiments. The fracture properties were studied by cutting membranes using a sharp knife mounted on a specially designed fixture. Again, various temperature and humidity conditions were used, and the fracture energy of the membranes was recorded as a function of cutting rate. Fracture energy master curves with respect to reduced cutting rates were constructed to get some idea about the intrinsic fracture energy of the membrane. The shift factors obtained from the fracture tests were found to match with those obtained from the stress relaxation experiments, suggesting that the knife cutting process is viscoelastic in nature. The rate and temperature dependence for these fracture energies are consistent with the rate, temperature, and moisture dependence of the relaxation modulus, suggesting the usefulness of a viscoelastic framework for examining and modeling durability of fuel cell membranes. The intrinsic fracture energy was initially thought to be a differentiating factor, which would separate various membranes tested in this study from one another. However, it was later found that all the membranes tested showed similar values at lower cutting rates, but showed significant variation at higher reduced cutting rates, and thus was thought to be a more meaningful region to differentiate the membranes for durability understanding. While the preceding work was undertaken to characterize as-received commercial PEMs, it is possible to modify material properties through treatment processes including thermal annealing and water treatment. The transient and dynamic viscoelastic properties of water-treated Nafion membranes revealed unusual behavior. Such unusual properties might have originated from irreversible morphological changes in PEM. Besides the constitutive viscoelastic properties, another set of properties useful for the stress modeling is the hygral strain induced as a function of relative humidity (RH) The effect of pretreatment on hygral strains induced as a function of RH was also investigated. These studies suggest that pretreatment significantly changes the mechanical properties of proton exchange membranes. / Ph. D.

Over the past three decades, the steady decrease in fossil energy resources, combined with a sustained increase in the demand for clean energy, has led the scientific community to develop new ways to produce energy. As is well known, one of the main challenges to overcome with fossil fuel-based energy sources is the reduction or even elimination of pollutant gases in the atmosphere. Although some advances have helped to slow the emission of greenhouse gases into the atmosphere (e.g., electric cars and more fuel-efficient gas-burning automobiles), most experts agree that it is not enough. Proton Exchange Membrane (PEM) fuel cells have been widely recognized as a potentially viable alternative for portable and stationary power generation, as well as for transportation. However, the widespread commercialization Proton Exchange Membrane Fuel Cells (PEMFCs) involves a thorough understanding of complex scientific and technological issues. This study investigated the various structure-property relationships and materials durability parameters associated with PEMFC development. First, the correlation between perfluorinated ionomer membranes and processing/performance issues in fuel cell systems was investigated. As confirmed by small-angle X-ray scattering data, impedance analysis, and dynamic mechanical analysis, solution processing with mixed organic-inorganic counterions was found to be effective in producing highly arranged perfluorinated sulfonic acid ionomer (PFSI) membranes with more favorable organization of the ionic domain. Moreover, thermal annealing was shown to enhance the proton mobility, thereby facilitating reorganization of the polymer backbone and the hydrophilic region for improved crystallinity and proton transport properties. This research also confirmed an increase in water uptake in the solution-processed membranes under investigation, which correlated to an increase in proton conductivity. Thus, annealing and solution-processing techniques were shown to be viable ways for controlling morphology and modulating the properties/performance of PFSI membranes. Second, this study investigated the role of the morphology on water and proton transport in perfluorinated ionomers. When annealed at high temperatures, a significant decrease in water uptake and an increase in crystallinity were observed, both of which are detrimental to fuel cell performance. Additionally, controlling the drying process was found to be crucial for optimizing the properties and performance of these membranes, since drying at temperatures close or above the α-relaxation temperature causes a major reorganization within the ionic domains. Third, although many investigations have looked at key PEMFC components, (e.g., the membrane, the catalyst, and the bipolar plates), there have been few studies of more "minor" components—namely, the performance and durability of seals, sealants, and adhesives, which are also exposed to harsh environmental conditions. When seals degrade or fail, reactant gases leak or are mixed, it can degrade the membrane electrode assembly (MEA), leading to a performance decrease in fuel cell stack performance. This portion of the research used degradation studies of certain proprietary elastomeric materials used as seals to investigate their overall stability and performance in fuel cell environments with applied mechanical stresses. Additionally, characterization of the mechanical and viscoelastic properties of these materials was conducted in order to predict the durability based on accelerated aging simulations as well. Continuous stress relaxation (CSR) characterization was performed on molded seals over a wide range of aging conditions using a customized CSR fixture. The effects of temperature, stress, and environmental conditions are reported in terms of changes in momentary and stress relaxations, chain scission and secondary crosslink formation. Aging studies provided insights on how anti-degradants or additives affect the performance and properties of sealing materials, as well as how a variety of environmental considerations might be improved to extend the lifetime of these elastomers. / Ph. D.

Cette thèse apporte des éléments sur la compréhension de la gestion de l'eau et de ses effets sur les performances électriques d'une PEMFC au moyen de modélisations multi-échelle des transferts. Une analyse du transport couplé de charges et de matière dans les pores de la membrane est proposée. La présence d'eau liquide est prise en compte dans les GDL (écoulements diphasiques) et les couches actives (noyage). Le couplage de ces modèles à une description des transferts de matière le long des canaux d’alimentation permet de mettre en évidence une répartition non-uniforme des concentrations en eau, des flux et donc de la densité de courant. Les résultats numériques sont comparés à des données expérimentales (coefficient de partage de l'eau et performance électrique locale) obtenues au laboratoire sur deux piles. Ceci permet de valider les modèles de fonctionnement du cœur de pile et d'alimenter la réflexion sur la connaissance et la modélisation des transferts d'eau dans le cœur de pile / This works contributes to the understanding of water management of polymer electrolyte membrane fuel cell and of its links with the electrical performances. More specifically, the manuscript deals with the multi-scale modelling of transport phenomena. An analysis of coupled mass and charge transfer in the pores of a polymer membrane is presented. The presence of liquid water is considered in the GDL (two-phase flow) and in the active layers (flooding). The description of these phenomena is associated with that of gas depletion along the bipolar plate channels. This allows to emphasize the non-uniformity of water concentration, of the fluxes and as a consequence, of current density. The numerical results are compared with experimental data (water transport coefficient, local electrical performances) measured on two different fuel cells. This comparison validates at least partially the numerical models and provides further information for the analysis of water management within PEMFC

Nous avons étudié les mécanismes de dégradation de catalyseurs Pt3Co/C en conditions réelles (stacks 16 cellules, hydrogène/air, stationnaire et intermittent, t > 1000 heures). Des modifications de la structure atomique, de la morphologie et de la composition chimique des catalyseurs ont été mises en évidence grâce à des techniques à résolution atomique, tels que la microscopie HAADF ou encore la spectroscopie d'absorption de rayons X. En plus d'être sujets à la maturation d'Ostwald 3D, ces catalyseurs perdent continuellement et irréversiblement les atomes de cobalt contenus dans le matériau « natif », ce qui conduit à la formation de nanoparticules « creuses » de Pt. Nous avons montré l'effet d'une contamination de l'électrode par des cations métalliques (Co2+). Des hétérogénéités de vieillissement de ces électrodes, à la fois « dans le plan » et « à travers le plan », ont été mises en évidence, en utilisant des marqueurs structuraux caractéristiques des électrodes. Des différences locales des cinétiques et des mécanismes de dégradation ont été confirmées grâce à des tests en monocellule PEMFC à cathode segmentée. / The durability of Pt3Co/C PEMFC cathode catalysts is investigated under real operating conditions (16-cell short stacks, hydrogen/air, constant current or start/stop, ageing time > 1000 hours). Using atomically resolved physical techniques such as HRSTEM-HAADF, and XAS, a detailed picture of how atomic structure, chemical composition and morphology of these cathode catalysts are changing over time has been drawn. In addition to 3D Ostwald ripening, these Pt-alloy catalysts undergo irreversible decrease of their cobalt content upon aging, yielding formation of “hollow” Pt/C nanoparticles. In the meantime, a great amount of Co2+ species is released within the MEA, which influences the catalyst surface reactivity and its ORR activity. Finally, structural markers of the degradation of the cathode catalyst have been used to unveil aging heterogeneities within the MEA: “through-the-plane” heterogeneities of aging (i.e. from the PEM/cathode interface to the cathode/GDL interface), and “in-the-plane” heterogeneities of ageing (i.e. from the gas inlet to the gas outlet) have been evidenced. The latter was confirmed using a cathode catalytic layer segmented in 20 segments along the gas flow channel.

Les piles à combustible à membrane échangeuse de protons sont des dispositifs de conversion de l’énergie propre et efficace. Les gammes de puissance accessibles permettent leur utilisation dans le domaine de transport et des applications stationnaires. Il existe deux verrous technologiques à lever pour le déploiement de la cathode:i) Diminution de la quantité de platine dans le catalyseur.ii) l'amélioration de la stabilité du support de catalyseur à haut potentiel. Dans ce travail, nous présentons deux stratégies qui permettent de faire face à ces problématiques et améliorer les performances et la durabilité des cathodes: développer de nouveaux électrocatalyseurs à très faible quantité de platine et des supports à base de matériaux résistants à la corrosion.Afin de réduire la quantité de platine dans le catalyseur, nous avons développé des nanostructures fines de platine, qui permettent une exploitation électrocatalytique maximale et une quantité minimale de métal noble. Pour atteindre cet objectif, nous avons utilisé une méthode électrochimique basée sur le dépôt sous potentiel et le déplacement galvanique. Les nanostructures fines déposées sur le substrat modèle ont été caractérisées électrochimiquement ainsi que par des techniques microscopiques et d'analyse élémentaire.Pour réaliser un support résistant à la corrosion, notre approche a consisté en le remplacement du carbone noir conventionnel par un matériau conducteur d’oxyde d'étain dopé. Les matériaux à base de SnO2 ont démontré leur efficacité comme support électrochimique stable mais également efficace pour la réaction de réduction de l'oxygène. Dans cette étude, l’oxyde d’étain dopé au tantale a été préparé par électrofilage suivi d'une étape de calcination, permettent ainsi d’obtenir des fibres de morphologie tubulaires. Ces fibres ont été utilisées comme support de nanoparticules de platine préparées par la méthode de polyol assistée par micro-ondes, puis caractérisées pour leurs propriétés physico-chimiques et électrocatalytiques. En particulier, la stabilité aux cyclage en potentiel a été évaluée par analyse électrochimique ex situ. La possibilité d’associer l'électrocatalyseur à surface étendue avec les supports résistants à la corrosion pour obtenir des cathodes actives et durables est en cours. / Proton exchange membrane fuel cells are clean and efficient energy converters. Their accessible power ranges allow their use in the field of transport or stationary applications. Two main challenges concern the cathode deployment:i) The reduction of the amount of low abundant platinum group metal in the catalyst.ii) The enhancement of stability of the catalyst support at high voltage.In this work we present two strategies to address these challenges and improve performance and durability of the cathodes: developing novel ultra-low loaded platinum electrocatalysts and corrosion resistant support materials.To reduce noble metal amount in the catalyst, we developed platinum thin films, which allow maximal electrocatalytic exploitation thus minimal loading. For that, we have used electrochemical methods based on under-potential deposition and galvanic displacement. The thin structures deposited on model substrates were characterized by electrochemical, elemental analysis and microscopy techniques.To prepare corrosion resistant supports, our strategy was the replacement of conventional carbon black with a doped conducting tin oxide. SnO2-based materials have been demonstrated as electrochemical stable supports also promoting platinum activity for the oxygen reduction reaction. In this work, tantalum-doped tin oxide was prepared by electrospinning followed by calcination, leading to a fiber-in-tube morphology. This support was catalyzed with platinum nanoparticles prepared by a microwave-assisted polyol method, and characterized for their physico-chemical and electrocatalytic properties. In particular, stability to voltage cycling was evaluated by ex situ electrochemical analysis.The possibility to associate the extended surface electrocatalyst with the corrosion resistant supports to obtain active and durable cathodes is in progress.

Sistemas de PEMFC são capazes de gerar energia elétrica com alta eficiência e baixa ou nenhuma emissão de poluentes, porém questões de custo e durabilidade impedem sua ampla comercialização. Nesse trabalho foi desenvolvido um MEA com eletrocatalisadores à base de paládio. Foram sintetizados e caracterizados eletrocatalisadores Pd/C, Pt/C e Ligas PdPt/C com diferentes razões entre metais e carbono. Foi realizado um estudo da razão entre ionômero de Nafion e eletrocatalisador para formação de triplas fases reacionais de máximos desempenhos, criado um modelo matemático para transpor esse ajuste para eletrocatalisadores com diferentes razões entre metal e suporte, considerando os aspectos volumétricos da camada catalisadora, e então realizado um estudo da espessura da camada catalisadora. Para as caracterizações foram utilizadas as técnicas de Difração de Raios-X, Microscopias Eletrônicas de Transmissão e de Varredura, Energia Dispersiva de Raios-X, Picnometria a Gás, Porosimetria por Intrusão de Mercúrio, Adsorção de Gás, segundo as equações de BET e BJH, Análise Termo Gravimétrica e feitas as determinações de diâmetros de partículas, de áreas de superfície específica e de parâmetros de rede. Todos os eletrocatalisadores foram usados no preparo de MEAs que foram avaliados em célula unitária de 5 cm2 entre 25 e 100 °C a 1 atm; e a melhor composição foi avaliada também a 3 atm. No estudo dos metais para as reações, visando reduzir a platina aplicada aos eletrodos, sem perdas de desempenho, foram selecionados Pd/C para ânodos e PdPt/C 1:1 para cátodos. A estrutura de MEA desenvolvida utilizou 0,25 mgPt.cm-2 e resultou em densidades de potência de até 550 mW.cm-2 e potências de até 2,2 kWe por grama de platina. A estimativa realizada mostrou que houve uma redução de até 64,5 % nos custos em relação à estrutura de MEA previamente conhecida. Em função da temperatura e pressão de operação foram obtidos valores a partir de R$ 3.540,73 para o preparo de MEAs para cada quilowatt instalado. Com base em estudos recentes, concluiu-se que o custo do MEA desenvolvido é compatível às aplicações estacionárias de PEMFC. / PEMFC systems are capable of generating electricity with high efficiency and low or no emissions, but durability and cost issues prevent its large commercialization. In this work MEA with palladium based catalysts were developed, Pd/C, Pt/C and alloys PdPt/C catalysts with different ratios between metals and carbon were synthesized and characterized. A study of the ratio between catalyst and Nafion Ionomer for formation of high performance triple-phase reaction was carried out, a mathematical model to implement this adjustment to catalysts with different relations between metal and support taking into account the volumetric aspects of the catalyst layer was developed and then a study of the catalyst layer thickness was performed. X-ray diffraction, Transmission and Scanning Electron Microscopy, X-ray Energy Dispersive, Gas Pycnometry, Mercury Intrusion Porosimetry, Gas adsorption according to the BET and BJH equations, and Thermo Gravimetric Analysis techniques were used for characterization and particle size, specific surface areas and lattice parameters determinations were also carried out. All catalysts were used on MEAs preparation and evaluated in 5 cm2 single cell from 25 to 100 °C at 1 atm and the best composition was also evaluated at 3 atm. In the study of metals for reactions, to reduce the platinum applied to the electrodes without performance losses, Pd/C and PdPt/C 1:1 were selected for anodes and cathodes, respectively. The developed MEA structure used 0,25 mgPt.cm-2, showing power densities up to 550 mW.cm-2 and power of 2.2 kWnet per gram of platinum. The estimated costs showed that there was a reduction of up to 64.5 %, compared to the MEA structures previously known. Depending on the temperature and operating pressure, values from US$ 1,475.30 to prepare MEAs for each installed kilowatt were obtained. Taking into account recent studies, it was concluded that the cost of the developed MEA is compatible with PEMFC stationary application.

Sistemas de PEMFC são capazes de gerar energia elétrica com alta eficiência e baixa ou nenhuma emissão de poluentes, porém questões de custo e durabilidade impedem sua ampla comercialização. Nesse trabalho foi desenvolvido um MEA com eletrocatalisadores à base de paládio. Foram sintetizados e caracterizados eletrocatalisadores Pd/C, Pt/C e Ligas PdPt/C com diferentes razões entre metais e carbono. Foi realizado um estudo da razão entre ionômero de Nafion e eletrocatalisador para formação de triplas fases reacionais de máximos desempenhos, criado um modelo matemático para transpor esse ajuste para eletrocatalisadores com diferentes razões entre metal e suporte, considerando os aspectos volumétricos da camada catalisadora, e então realizado um estudo da espessura da camada catalisadora. Para as caracterizações foram utilizadas as técnicas de Difração de Raios-X, Microscopias Eletrônicas de Transmissão e de Varredura, Energia Dispersiva de Raios-X, Picnometria a Gás, Porosimetria por Intrusão de Mercúrio, Adsorção de Gás, segundo as equações de BET e BJH, Análise Termo Gravimétrica e feitas as determinações de diâmetros de partículas, de áreas de superfície específica e de parâmetros de rede. Todos os eletrocatalisadores foram usados no preparo de MEAs que foram avaliados em célula unitária de 5 cm2 entre 25 e 100 °C a 1 atm; e a melhor composição foi avaliada também a 3 atm. No estudo dos metais para as reações, visando reduzir a platina aplicada aos eletrodos, sem perdas de desempenho, foram selecionados Pd/C para ânodos e PdPt/C 1:1 para cátodos. A estrutura de MEA desenvolvida utilizou 0,25 mgPt.cm-2 e resultou em densidades de potência de até 550 mW.cm-2 e potências de até 2,2 kWe por grama de platina. A estimativa realizada mostrou que houve uma redução de até 64,5 % nos custos em relação à estrutura de MEA previamente conhecida. Em função da temperatura e pressão de operação foram obtidos valores a partir de R$ 3.540,73 para o preparo de MEAs para cada quilowatt instalado. Com base em estudos recentes, concluiu-se que o custo do MEA desenvolvido é compatível às aplicações estacionárias de PEMFC. / PEMFC systems are capable of generating electricity with high efficiency and low or no emissions, but durability and cost issues prevent its large commercialization. In this work MEA with palladium based catalysts were developed, Pd/C, Pt/C and alloys PdPt/C catalysts with different ratios between metals and carbon were synthesized and characterized. A study of the ratio between catalyst and Nafion Ionomer for formation of high performance triple-phase reaction was carried out, a mathematical model to implement this adjustment to catalysts with different relations between metal and support taking into account the volumetric aspects of the catalyst layer was developed and then a study of the catalyst layer thickness was performed. X-ray diffraction, Transmission and Scanning Electron Microscopy, X-ray Energy Dispersive, Gas Pycnometry, Mercury Intrusion Porosimetry, Gas adsorption according to the BET and BJH equations, and Thermo Gravimetric Analysis techniques were used for characterization and particle size, specific surface areas and lattice parameters determinations were also carried out. All catalysts were used on MEAs preparation and evaluated in 5 cm2 single cell from 25 to 100 °C at 1 atm and the best composition was also evaluated at 3 atm. In the study of metals for reactions, to reduce the platinum applied to the electrodes without performance losses, Pd/C and PdPt/C 1:1 were selected for anodes and cathodes, respectively. The developed MEA structure used 0,25 mgPt.cm-2, showing power densities up to 550 mW.cm-2 and power of 2.2 kWnet per gram of platinum. The estimated costs showed that there was a reduction of up to 64.5 %, compared to the MEA structures previously known. Depending on the temperature and operating pressure, values from US$ 1,475.30 to prepare MEAs for each installed kilowatt were obtained. Taking into account recent studies, it was concluded that the cost of the developed MEA is compatible with PEMFC stationary application.