Membranas à base de polímeros perfluorosulfonados, como a Nafion, vêm sendo extensivamente usadas como membrana de troca protônica em células a combustível (FC). O objetivo deste trabalho foi desenvolver membranas eletrólito à base de polindeno sulfonado (SPInd) e poli(fluoreto de vinilideno) (PVDF), para uso como membranas de troca protônica em condições semelhantes às da membrana Nafion. As membranas foram preparadas por casting em diferentes composições utilizando PVDF como reforço mecânico e PVDF sulfonado (SPVDF) como agente compatibilizante. Todas as membranas foram avaliadas por análise termogravimétrica, calorimetria exploratória diferencial, análise dinâmico mecânica, microscopia eletrônica de varredura, grau de inchamento, capacidade de troca iônica e espectroscopia de impedância eletroquímica. As membranas com características semelhantes à membrana Nafion foram avaliadas em protótipo de FC a 80 °C. A membrana SPInd50/PVDF e as membranas com agente compatibilizante apresentaram condutividades iônicas na ordem de 10-2 S/cm, comparáveis àquela da membrana Nafion. A membrana com melhor desempenho em protótipo de FC foi o SPInd/PVDFC12, preparado com 50% de SPInd, 47,5% de PVDF e 2,5% de SPVDF (p/p), cujos valores de potencial de circuito aberto e densidade de potência máximo foram de 1,02 V e 74,54 mW/cm2, respectivamente. Apesar da densidade de potência máxima ser inferior à da membrana Nafion (603 mW/cm2), a membrana SPInd/PVDFC12 apresenta potencial para uso como eletrólito em célula a combustível. / Perfluorosulfonic acid ionomer membranes, e.g. Nafion, have been extensively used as proton exchange membranes in fuel cells (FC) due to their high proton conductivity and good mechanical properties. The aim of this work was to develop electrolyte membranes based on sulfonated polyindene (SPInd) and poly(vinylidene fluoride) (PVDF) to be used in the same conditions as Nafion. Membranes were prepared by casting with different compositions using PVDF as mechanical reinforcement and sulfonated PVDF (SPVDF) as coupling agent. The produced membranes were evaluated by thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis, scanning electron microscopy, water uptake, ion exchange capacity and electrochemical impedance spectroscopy. The membranes with similar results to Nafion, were evaluated in a FC prototype at 80 °C. The membrane SPInd50/PVDF and all the membranes with coupling agent had ionic conductivity in the order of 10-2 S/cm, comparable to the Nafion´s. The polyelectrolyte with the best performance was the SPInd/PVDFC12 which was prepared with 50 wt% SPInd, 47.5 wt% PVDF and 2.5 wt% SPVDF, that reached an open circuit voltage of 1.02 V and maximum power density of 74.54 mW/cm2. Even though Nafion´s maximum power density was higher (603 mW/cm2), the SPInd/PVDFC12 membrane showed potential to be used as electrolyte in fuel cells.

Membranas à base de polímeros perfluorosulfonados, como a Nafion, vêm sendo extensivamente usadas como membrana de troca protônica em células a combustível (FC). O objetivo deste trabalho foi desenvolver membranas eletrólito à base de polindeno sulfonado (SPInd) e poli(fluoreto de vinilideno) (PVDF), para uso como membranas de troca protônica em condições semelhantes às da membrana Nafion. As membranas foram preparadas por casting em diferentes composições utilizando PVDF como reforço mecânico e PVDF sulfonado (SPVDF) como agente compatibilizante. Todas as membranas foram avaliadas por análise termogravimétrica, calorimetria exploratória diferencial, análise dinâmico mecânica, microscopia eletrônica de varredura, grau de inchamento, capacidade de troca iônica e espectroscopia de impedância eletroquímica. As membranas com características semelhantes à membrana Nafion foram avaliadas em protótipo de FC a 80 °C. A membrana SPInd50/PVDF e as membranas com agente compatibilizante apresentaram condutividades iônicas na ordem de 10-2 S/cm, comparáveis àquela da membrana Nafion. A membrana com melhor desempenho em protótipo de FC foi o SPInd/PVDFC12, preparado com 50% de SPInd, 47,5% de PVDF e 2,5% de SPVDF (p/p), cujos valores de potencial de circuito aberto e densidade de potência máximo foram de 1,02 V e 74,54 mW/cm2, respectivamente. Apesar da densidade de potência máxima ser inferior à da membrana Nafion (603 mW/cm2), a membrana SPInd/PVDFC12 apresenta potencial para uso como eletrólito em célula a combustível. / Perfluorosulfonic acid ionomer membranes, e.g. Nafion, have been extensively used as proton exchange membranes in fuel cells (FC) due to their high proton conductivity and good mechanical properties. The aim of this work was to develop electrolyte membranes based on sulfonated polyindene (SPInd) and poly(vinylidene fluoride) (PVDF) to be used in the same conditions as Nafion. Membranes were prepared by casting with different compositions using PVDF as mechanical reinforcement and sulfonated PVDF (SPVDF) as coupling agent. The produced membranes were evaluated by thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis, scanning electron microscopy, water uptake, ion exchange capacity and electrochemical impedance spectroscopy. The membranes with similar results to Nafion, were evaluated in a FC prototype at 80 °C. The membrane SPInd50/PVDF and all the membranes with coupling agent had ionic conductivity in the order of 10-2 S/cm, comparable to the Nafion´s. The polyelectrolyte with the best performance was the SPInd/PVDFC12 which was prepared with 50 wt% SPInd, 47.5 wt% PVDF and 2.5 wt% SPVDF, that reached an open circuit voltage of 1.02 V and maximum power density of 74.54 mW/cm2. Even though Nafion´s maximum power density was higher (603 mW/cm2), the SPInd/PVDFC12 membrane showed potential to be used as electrolyte in fuel cells.

Orientador: Wagner dos Santos Oliveira / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-02T13:01:07Z (GMT). No. of bitstreams: 1 Souza_ViniciusRicardode_M.pdf: 5087609 bytes, checksum: 86dd0a3a9b59a2601d2f14847b4a419f (MD5) Previous issue date: 2002 / Resumo: Um dos desenvolvimentos atuais mais significativos em sistemas energéticos está na área das células de combustível. Estes dispositivos que geram energia elétrica combinando hidrogênio (ou hidrocarbonetos) com o oxigênio do ar, apresentam-se como fortes vetores de desenvolvimento científico-tecnológico, que apontam no sentido de substituírem os motores à combustão interna na área dos transportes, assim como para gerar energia elétrica de um modo limpo e eficiente, dentro de um novo mercado, o da geração distribuída. O início das pesquisas em células de combustível ocorreu há mais de 150 anos, por William Grove, mas apenas nos últimos 15 anos, com o grande desenvolvimento na área de materiais, foi que a tecnologia em células e pilhas de combustível tomou-se bastante promissora no cenário energético mundial. É nesse contexto que surge o objetivo deste trabalho, levando em conta estudos e o desenvolvimento do Projeto Básico de uma Célula de Combustível de Eletrólito Polimérico (PEMFC), além de mostrar alguns campos de atuação que oferecem, já como dispositivos comercialmente viáveis, e servindo a sociedade. Considerou-se para tal a literatura especializada, com o projeto sendo construído a partir de software gráfico apropriado. Fezse também uma análise crítica dos dados disponíveis na literatura, anexando-se Folhas de Dados contendo especificações dos componentes da célula. Examinou-se a função de cada componente da célula, descrevendo os processos quimicos, e eletroquimicos que ocorrem neste reator assim como, as suas variáveis de projeto e de processo. Os muitos avanços alcançados no desenvolvimento tecnológico das PEMFC, principalmente no decorrer da década de 90, e a partir dela, através do esforço conjunto entre entidades governamentais e a indústria de vários países, demonstraram a viabilidade comercial desses geradores de energia, principalmente nas aplicações móveis. Assim, em um futuro determinista e imediato, as PEMFC se tornarão realidade como geradores de energia de alta eficiência e, de baixa emissão de poluentes, contribuindo para o desenvolvimento de uma sociedade mais comprometida com os impactos ambientais da geração e consumo de energia, posta a seu serviço e bem estar. As pilhas de combustível devem ser o marco inicial da denominada Era do Hidrogênio / Abstract: One of the most significant recent developments in energy systems is in the area from the fuel ceils. These devices that generate electric energy combining hydrogen (or hydrocarbons) with the oxygen of the air as fortresses vectors of scientific-technological development, that aim in the sense of replace the motors to the internal combustion in the area of the transports, as well as for generate electric energy of a way c1ean and efficient, inside a news market, the from the generation distributed. The beginning from the researches from fuel cells occurred there is more of 150 years, by William Grove, but barely in the last 15 years, with the big development in the area of stuff, went that to technology in ceIls and stacks of fuel cells became promising enough in the world energy setting. It is in that context that the objective of this arises work, leading in count studies and the development of the Project Basic of an Proton Exchange Membrane Fuel Cell (PEMFC), beyond show some fields of action that they offer, already as commercially viable devices, and serving to society. For such, to literature specialized is consult, with the project being built from graphic software appropriated. Make also an analysis critic of the data available in the literature, enclosing Data Sheets, contained specifications of the components from the cell. This work examine the function of each component from the ceIl, describing the chemical and electrochemical reaction that occur in this reator as well as, theirs variables of project and of process. The many advancements achieved in the technological development of the PEMFC, mainly in elapse from the decade of 90, and from of the joint effort between govemmental entities and to industry of several countries, showed to commercial feasibility of those generators of energy, mainly in the automobile application. Like this, in a future immediate, the PEMFC will become reality as generators of energy of high efficiency and, of pollutants emission decrease, contributing for the development of a more committed society with the environmental impacts from the generation and consume of energy, places to its service and comfort The stacks of fuel cell should be the initial landmark from the named Age of Hydrogen / Mestrado / Ciencia e Tecnologia de Materiais / Mestre em Engenharia Química

The performance of PEM fuel cells (PEMFC) relies on the proper control and management of the liquid water that forms as a result of the electrochemical process, especially at high current densities. The liquid water transport and removal process in the gas flow channel is highly dynamic and many of its fundamental features are not well understood. This thesis presents an experimental and theoretical investigation of the emergence of water droplets from a single pore into a microchannel. The experiments are performed in a 250 µm × 250 µm air channel geometry with a single 50 µm pore that replicates a PEMFC cathode gas channel. A droplet manipulation platform is constructed using a microfluidics soft lithographic process to allow observation of the dynamic nature of the water droplets. Flow conditions that correspond to typical operating conditions in a PEMFC are selected. A test matrix of experiments comprised of different water injection velocities and air velocities in the gas microchannel is studied. Emergence, detachment and subsequent dynamic evolution of water droplets are analyzed, both qualitatively and quantitatively. Quantitative image analysis tools are implemented and applied to the time-resolved images to document the time evolution of the shape and location of the droplets, characteristic frequencies, dynamic contact angles, flow regime and stability maps. Three different flow regimes are identified, slug, droplet, and film flow. The effects of the air flow rate and droplet size on the critical detachment conditions are also investigated. Numerical simulations using Volume-of-Fluid method are presented to investigate the water dynamics in the droplet flow. The focus of the modeling is on methods that account for the dynamic nature of the contact line evolution. Results of different approaches of dynamic contact angle formulations derived empirically and by using the theoretically based Hoffmann function are compared with the static contact angle models used to date. The importance of the dynamic formulation as well as the necessity for high numerical resolution is highlighted. The Hoffmann function implementation is found to better capture the salient droplet motion dynamics in terms of advancing and receding contact angle and periodicity of the emergence process. To explore the possibility of using the pressure drop signal as a diagnostic tool in operational fuel cells that are not optically accessible, a flow diagnostic tool was developed based on pressure drop measurements in a custom designed two-phase flow fixture with commercial flow channel designs. Water accumulation at the channel outlet was found to be the primary cause of a low-frequency periodic oscillation of pressure drop signal. It is shown that the flow regimes can be characterized using the power spectrum density of the normalized pressure drop signal. This is used to construct a flow map correlating pressure drop signals to the flow regimes, and opens the possibility for practical flow diagnostics in operating fuel cells. / Graduate

Cette thèse réalisée dans le cadre des projets PIE CNRS AMELI-0Pt et AMEPlas et ANR AMADEUS a regroupé plusieurs entités autour de la thématique des piles à combustible : Dreux Agglomération puis l’Agence Innovation Made In Dreux (MID), le GREMI, le LACCO et initialement l’industriel MHS Equipment. L’objectif de ce travail est l’élaboration par voie plasma et l’optimisation d’électrodes de piles à combustible de type PEMFC et SAMFC dans le but d’obtenir de bonnes performances avec des charges de platine ultra faibles ou sans platine. Le projet a été organisé en quatre étapes : l’étude de la croissance simultanée de platine et de carbone co-pulvérisés par plasma, la dispersion optimale de quantités ultra faibles de catalyseur, le remplacement du platine par un alliage bimétallique à base de palladium, et le dépôt direct du catalyseur sur la membrane par plasma. En utilisant un faisceau synchrotron de rayons X (Synchrotron SOLEIL), en collaboration avec le CRMD, l’étude GISAXS des couches minces Pt-C co-pulvérisés a révélé l’organisation particulière du platine dans ce type de nanostructure. Ces couches minces Pt-C offrent d’excellentes performances (20 kW.gPt-1) avec des charges de platine ultra faibles. Des électrodes PdPt (5 %at Pt) faiblement chargées permettent d’atteindre de bonnes performances en PEMFC quasiment sans platine (12,5 kW.gPd-1 et 250 kW.gPt-1). L’étude de l’activité de catalyseurs PdAu vis-à-vis de l’oxydation du glycérol a révélé l’origine des effets synergiques du palladium et de l’or en milieu alcalin. Le dépôt plasma direct de platine associé ou non au dépôt de carbone sur membrane a été optimisé. Les performances obtenues avec des CCM (Catalyst Coated Membrane) plasma démontrent l’intérêt de ce type d’architecture. / This research work has been achieved in the context of the PIE CNRS AMELI-0Pt and AMEPlas and ANR AMADEUS projects and has gathered several entities around the Fuel Cell research: Dreux Agglomération and Agence Innovation Made In Dreux (MID), the French national research laboratories GREMI and LACCO and initially the company MHS Equipment. The project aims at developing and optimising fuel cell electrodes (anode and cathode) for PEMFC (Proton Exchange Membrane Fuel Cell) and SAMFC (Solide Alkaline Membrane Fuel Cell) entirely by plasma in order to reach effective performances with ultra low platinum loadings or none at all. The project was divided into four stages: the study of the simultaneous growth of platinum and carbon co-sputtered by plasma, the optimum dispersion of a very small amount of catalysts, the replacement of platinum by a palladium based bimetallic alloy, and the direct deposition of the catalyst on the polymer membrane by plasma sputtering. By using an X-ray synchrotron beam light source (SOLEIL Synchrotron), in collaboration with the CRMD, the GISAXS study of co-sputtered Pt-C thin films has revealed the particular organisation of platinum inside this type of nanostructure. These Pt-C thin films offer excellent performances (20 kW.cm-2) with ultra low platinum amounts. Low loaded PdPt (5 %at Pt) electrodes offered good performances almost without platinum (12,5 kW.gPd-1 et 250 kW.gPt-1). The study of the activity of PdAu catalysts (plasma sputtered) on the glycerol electro-oxidation revealed the origin of the synergistic effects of palladium and gold in an alkaline medium. The direct plasma deposition of platinum associated or not with carbon deposition on membrane has been optimised. The performances of the plasma prepared CCM (Catalyst Coated Membrane) demonstrate the potential of this type of architecture.

Direct membrane deposition (DMD) was recently introduced as a novel polymer electrolyte membrane fabrication method. Here, this approach is extended to fabricate 12 μm thin nanocomposite fuel cell membranes. Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) nanofibers are directly electrospun onto gas diffusion electrodes. By inkjet-printing Nafion ionomer dispersion into the pore space of PVDF-HFP nanofiber mats, composite membranes of 12 μm thickness were fabricated. At 120 °C and 35% relative humidity, stoichiometric 1.5/2.5 H2/air flow and atmospheric pressure, the power density of the DMD fuel cell (0.19 W cm-2), was about 1.7 times higher than that of the reference fuel cell (0.11 W cm-2) with Nafion HP membrane and identical catalyst. A lower ionic resistance and, especially at 120 °C, a reduced charge transfer resistance is found compared to the Nafion HP membrane. A 100 h accelerated stress test revealed a voltage decay of below 0.8 mV h-1, which is in the range of literature values for significantly thicker reinforced membranes. Finally, this novel fabrication approach enables new degrees of freedom in the design of complex composite membranes. The presented combination of scalable deposition techniques has the potential to simplify and thus reduce cost of composite membrane fabrication at a larger scale.

We show that the combination of direct membrane deposition with proton conductive nanofiber reinforcement yields highly durable and high power density fuel cells. Sulfonated poly(ether ketone) (SPEK) was directly electrospun onto gas diffusion electrodes and then filled with Nafion by inkjet-printing resulting in a 12 μm thin membrane. The ionic membrane resistance (30 mΩ*cm2) was well below that of a directly deposited membrane reinforced with chemically inert (PVDF-HFP) nanofibers (47 mΩ*cm2) of comparable thickness. The power density of the fuel cell with SPEK reinforced membrane (2.04 W/cm2) is 30% higher than that of the PVDF-HFP reinforced reference sample (1.57 W/cm2). During humidity cycling and open circuit voltage (OCV) hold, the SPEK reinforced Nafion membrane showed no measurable degradation in terms of H2 crossover current density, thus fulfilling the target of 2 mA/cm2 of the DOE after degradation. The chemical accelerated stress test (100 h OCV hold at 90 °C, 30% RH, H2/air, 50/50 kPa) revealed a degradation rate of about 0.8 mV/h for the fuel cell with SPEK reinforced membrane, compared to 1.0 mV/h for the PVDF-HFP reinforced membrane.

Proton Exchange Membrane Fuel Cell (PEMFC) is the most commonly used type of hydrogen fuel cell and a promising solution for vehicular and stationary power applications. This research starts with an extensive review of the PEMFC research, including experimental testing, and performance modeling, and performance degradation modeling using relatively accurate and easy-to-use mechanistic models. Next, a new PEMFC performance degradation model is introduced by amending the semi-empirical, mechanistic performance model to support the design and control of PEMFC systems and fuel cell electric vehicles (FCEVs). The new model takes into account critical factors impacting PEMFC performance. The performance degradation due to the oxidation of catalyst platinum (Pt) and loss of active surface area is captured by fitting the degradation model parameters using experimental data to capture the observed PEMFC performance fading. The new performance degradation model is then tested and further improved under the four typical load modes that a PEMFC system experiences in a vehicular application under regular driving cycles. The model is also fitted with PEMFC experimental degradation data under different load modes to improve modeling accuracy. The new model is applied and tested using simulations of a representative FCEV. The actual power load on an 80 kW PEMFC system in the modeled FCEV was obtained using the Advanced Vehicle Simulator (ADVISOR) under the US EPA Urban Dynamometer Driving Schedule (UDDS). With the ability to predict the operation life of the PEMFC, the appropriate sizes of the PEMFC system and the energy storage system (ESS) can be determined. Improved power control and energy management can be developed to extend the operation life of the PEMFC and lower the lifecycle cost of the FCEV. / Graduate

Title: Study of new catalytic materials for proton exchange membrane fuel cells Author: Petr Homola Department: Department of Surface and Plasma Science Supervisor: Prof. RNDr. Vladimír Matolín, DrSc. Abstract: Submitted thesis deals with study of thin layers based on platinum and cerium oxides in order to use them in fuel cells with polymer membrane (PEM- FC). A set of samples with different amount of platinum was prepared by means of magnetron sputtering. Samples were investigated by X - ray Photoelectron Spectroscopy (XPS) and results were confronted with sputtering parameters. It was found out that chemical state of platinum is related to its amount in thin layer. The less platinum was contained in thin layer, the less amount of Pt0 state was observed and amounts of Pt2+ and Pt4+ states increased. Furthermore the temperature stability of prepared layers in the interval from room temperature to 250 ◦ C was studied by means of XPS. The adsorption of carbon monoxide was measured by infrared absorption spectroscopy (IRAS). Increasing degree of adsorption on sample probably related to platinum reduction with increased tem- perature was observed. Measurements of other samples were devaluated by strong contamination with nickel carbonyls. Keywords: PEMFC, cerium oxide, magnetron sputtering, XPS, CO adsorption

The purpose of this project was the modeling, optimization and prediction of a hybrid system composed of a fuel cell, a dc-dc converter and a supercapacitor in series. Lab tests were performed for each device to understand their behavior, and then each one was modeled using software (Simulink). The validation of the model was done by comparing its results with measured data; finally the model was used for the optimization and the prediction of the hybrid system