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The gas diffusion layer (GDL) is one of the key components in a polymer electrolyte membrane (PEM) fuel cell. It performs several functions including the transport of reactant gases and product water to and from the catalyst layer, conduction of both electrons and heat produced in the catalyst layer, as well as mechanical support for the membrane. The overarching goal of this work is to thoroughly examine the GDL structure and properties for use in PEM fuel cells, and more specifically, to determine how to characterize the GDL experimentally ex-situ, to understand its performance in-situ, and to relate theory to performance through controlled experimentation. Thus, the impact of readily measured effective water vapor diffusivity on the performance of the GDL is investigated and shown to correlate to the wet limiting current density, as a surrogate of the oxygen diffusivity to which it is more directly related. The influence of microporous layer (MPL) design and construction on the fuel cell performance is studied and recommendations are made for optimal MPL designs for different operating conditions. A method for modifying the PTFE (Teflon) distribution within the GDL is proposed and the impact of distribution of PTFE in the GDL on fuel cell performance is studied. A method for characterizing the surface roughness of the GDL is developed and the impact of surface roughness on various ex-situ GDL properties is investigated. Finally, a detailed analysis of the physical structure and permeability of the GDL is provided and a theoretical model is proposed to predict both dry and wet gas flow within a GDL based on mercury intrusion porosimetry and porometry data. It is hoped that this work will contribute to an improved understanding of the functioning and structure of the GDL and hence advance PEM fuel cell technology.

Os componentes do conjunto membrana/eletrodos (MEA) das células a combustível de membrana de eletrólito polimérico/Polymer Electrolyte Membrane Fuel Cells (PEMFC) são sensíveis a impurezas, as quais podem vir do ar, do gás combustível e/ou da degradação dos componentes do módulo. Amônia, sulfeto de hidrogênio e monóxido de carbono são juntos os três principais subprodutos cotaminadores nos processos de geração de hidrogênio por reforma de combustíveis. Estes contaminadores afetam negativamente o desempenho das PEMFCs, assim é importante o entendimento destes efeitos para mitigá-los e introduzir a tecnologia das PEMFCs no mercado consumidor. Desta forma experimentos foram realizados visando diagnosticar os efeitos da amônia e do sulfeto de hidrogênio sobre os componentes do MEA das PEMFCs. Para a contaminação por sulfeto de hidrogênio foi provado, utilizando-se da técnica de cromatografia gasosa e de stripping, que a contaminação ocorre através da interação química e eletroquímica do contaminador com a superfície do catalisador de platina, e que estas interações ocorrem via um processo dissociativo e um processo oxidativos respectivamente. Estes processos de interação geram enxofre adsorvido sobre a superfície da platina, a qual é bloqueada para posterior oxidação de hidrogênio, gerando sobrepotenciais que reduzem a diferença de potencial da célula. Utilizando-se da técnica de cromatografia gasosa e agora de voltametria cíclica foi mostrado na PEMFC, que durante o processo de remoção do enxofre adsorvido a platina dióxido de enxofre é gerado. Ainda na PEMFC, foi mostrado utilizando-se da técnica de \"air bleed\" que maiores tolerâncias ao sulfeto de hidrogênio podem ser alcançadas, apesar de ser insignificante. Para o caso da contaminação da PEMFC por amônia, indiretamente foi mostrado, utilizando-se técnicas eletroquímicas solução de ácido perclórico, que amônia pode afetar a reação de redução de oxigênio pela sua adsorção sobre a superfície do catalisador, ou pelo bloqueio da mesma para posterior adsorção/redução de oxigênio. Em estudos de absorção de água e condutividade de membranas de NafionTM, sob diferentes frações catiônicas (prótons/amônio), em contato com água na fase vapor sob diferentes atividades, foi mostrado que quanto maior a concentração de íons contaminadores no eletrólito menor a quantidade de água absorvida e menor a condutividade da membrana. Também foi mostrado que se tais membranas fossem usadas como eletrólito em PEMFCs, o desempenho da célula seria afetado drasticamente por perdas ôhmicas. Também foi mostrado que sob contaminação por amônia, PEMFCs sofrem aumentos em resistências ôhmicas devido a reduções na condutividade do eletrólito, contudo foi provado que esta representa menos de dez por cento do total de perdas observadas no desempenho da célula. Desde estudo foi concluído que amônia afeta o desempenho das PEMFCs principalmente pela redução na atividade dos prótons na camada catalítica catódica, que causa reduções no potencial misto de equilíbrio da reação de redução de oxigênio, e portanto na diferença de potencial da célula. Finalmente foi provado indiretamente que amônia deixa a célula através do equilíbrio de amônio com água, o qual deslocado gera amônia, a qual deixa a célula junto com o fluxo de gás cotódico. / The Membrane Electrode Assembly components of a PEMFC are sensitive to impurities, which can came with the air or hydrogen stream, or from the degradation of the stack components. Ammonia, hydrogen sulfide and carbon monoxide are together the main sub-products of fuel reforming processes for generating hydrogen. These contaminants negatively affect the PEMFC performance, so it is important to understand what those effects are in order to mitigate them and introduce PEMFC technology in the mass market. Therefore, experiments were carried out to diagnose the effects hydrogen sulfide and ammonia have on the MEA components of PEMFCs. For contamination by hydrogen sulfide it was proved utilizing EMS and stripping techniques that the poisoning process happens by chemical and electrochemical interactions of the contaminant with the Platinum catalyst surface, and that these interactions happen by a dissociative and oxidative process, respectively. Those processes generate sulfur adsorbed on the Platinum surface, which blocks it for further hydrogen oxidation, generating overpotentials, which reduce the cell potential. Utilizing the EMS and now the cyclic voltammetry technique it was shown that during the process of removing sulfur from the Platinum surface one generates sulfur dioxide. Using the Air Bleed technique it was shown that higher tolerances of the PEMFC against hydrogen sulfide can be reached, despite being insignificant. For contamination of the cell by ammonia it was indirectly proved utilizing electrochemical techniques in perchloric acid solutions that ammonia can affect the oxygen reduction reaction by adsorbing on the catalyst surface, or by blocking the surface for further oxygen adsorption/reduction. Studying water uptake and ionic conductivity of Nafion membranes under many different cation fractions (proton/ammonium) in contact with water vapor at different temperatures and water activities, it was proved that the more ammonium one has in the membrane the less will be the water uptake and ionic conductivity of it. It was also shown that if those membranes were used as electrolyte in PEMFC the cell performance would be severely affected by ohmic losses. It was also shown that under ammonia exposure PEMFCs suffer by ohmic resistance increases due to the lowering in the ionic conductivity of the electrolyte, however it was proved that it represent less than ten percent of the observed losses in the cell performance. From this study it was concluded that ammonia mainly affect the PEMFC performance by lowering the cathode catalyst layer proton activity, which lowers the oxygen reduction reaction equilibrium potential, and then the cell potential. Finally it was indirectly proved that ammonia leaves the cell by the equilibrium of ammonium and water, which dislocated generates ammonia that leaves the cell together with the cathode gas stream.

O presente trabalho apresenta a preparação e caracterização de eletrólitos poliméricos nanocompósitos (NPEs - Nanocomposite Polymer Electrolytes) obtidos a partir da argila montmorilonita e goma gelana para aplicação em janelas eletrocrômicas. Para verificar a influência de argila nas propriedades físicas e químicas de nanocompósitos, incialmente foram preparadas membranas a base de goma gelana dos tipos low acyl (CGLA) ou high acyl (CGHA) contendo etilenoglicol ou glicerol como plastificantes e quantidades diferentes de LiClO4 (perclorato de lítio) como doador de cátions Li+. A caracterização por espectroscopia de impedância eletroquímica revelou que o eletrólito de goma gelana tipo low acyl (CGLA), com glicerol como plastificante e 0,40 g de LiClO4 (GGLA-G40) apresentava a condutividade iônica mais elevada entre as amostras, cujos valores ficaram entre 2,14 x 10-6 S/cm a 30 °C e 3,10 x 10-4 S/cm a 80°C. Ela foi usada para a preparação de nanocompósitos através de adição de quantidades diferentes de argila montmorilonita liofilizada Na+SYN-1 (synthetic mica-montmorillonite). O eletrólito com a melhor condutividade de 1,86 x 10-5 S/cm a 30°C e 3,74 x 10-4 S/cm à temperatura de 80°C continha 0,10 g de argila Na+SYN-1 (GG-MMT10). Essa mesma membrana apresentou uma transmitância entre 23% e 42% na faixa do visível, além de refletância no UV de 22% e 13% no visível. O difratograma de raios-X mostrou que os nanocompósitos formaram uma estrutura predominantemente intercalada e intercalada-floculada. Os termogramas revelaram que a estabilidade térmica dos eletrólitos não sofreu praticamente quase nenhuma alteração com a incorporação de argila. A morfologia microscópica apontou uma superfície não homogênea. Por fim, os ECDs transmissivos de configuração vidro/ITO/PB/eletrólito de goma gelana-Na+SYN-1/CeO2-TiO2/ITO/vidro montados usando o nanocompósito GG-MMT10 exibiram uma variação de transmitância no visível de 4%, indicando que esse material não apresenta benefícios em aplicações envolvendo janelas eletrocrômicas. / This work presents the preparation and characterization of nanocomposite polymer electrolytes (NPEs) obtained from montmorillonite clay and gellan gum for application in electrochromic devices. Initially, we produced membranes by using low (CGLA) and high acyl (CGHA) gellan gum, ethylene glycol or glycerol as plasticizers and different amounts of LiClO4 as a Li+ donor. Electrochemical impedance spectroscopy indicated that the sample with low acyl gellan gum (CGLA), glycerol as plasticizer and 0.40 g of LiClO4 (GGLA-G40) showed the highest conductivity of 2.14 x 10-6 S/cm at 30 °C and 3.10 x 10-4 S/cm at 80°C. This sample was used to obtain a NPE by addition of different amounts of lyophilized montmorillonite clay Na+SYN-1 (synthetic mica-montmorillonite). The sample with 0.10 g of Na+SYN-1 clay (GG -MMT10) showed the best conductivity of 1.86 x 10-5 S/cm at 30°C and 3.74 x 10-4 S/cm at 80°C. This membrane transmitted between 23% and 42% in the visible range (wavelength 400 nm to 800 nm), and had reflectance of 22% and 13% in the UV and Vis, respectively. The X-ray diffraction indicated that the nanocomposites formed a predominantly intercalated or intercalated-flocculated structure. The thermograms revealed that the thermal stability of the electrolytes does not change with the incorporation of clay, and the microscopic morphology indicated a non-homogeneous surface. Finally, the transmissive ECDs with glass/ITO/PB/gelan gum-Na+SYN-1 electrolyte/CeO2-TiO2/ITO/glass configuration, assembled using the sample GG-MMT10 exhibited a visible transmittance variation of 4%, indicating that this NPE is not suitable for electrochromic devices application.

As células eletroquímicas emissoras de luz (PLECs) pertencem a um novo ramo importante na optoeletrônica orgânica devido ao seu grande potencial para ser usado como ponto - pixels para telas coloridas e também para painéis de iluminação. Diferentemente de diodos orgânicos emissores de luz (OLEDs), a tecnologia de OLECs ainda está em estágios iniciais de desenvolvimento, em comparação com a tecnologia de OLED , OLECs tem a vantagem de ser operado em ambas as polaridades de tensão ( para a frente ou de polarização reversa ), e, além disso, o seu desempenho é menos dependente dos materiais do eletrodos e a espessura da camada ativa do dispositivo. A camada ativa de um OLEC compreende uma mistura de um polímero eletroluminescente conjugado e um eletrólito de polímero. Consequentemente, o transporte elétrico durante a operação do dispositivo envolve uma combinação de dinâmica iônica e eletrônica e efeitos intrincados nas interfaces com os eletrodos. A literatura apresenta até agora duas abordagens diferentes para descrever o fenômeno de transporte nas OLECs. O modelo de eletrodinâmica, que combina separação iônica com o processo de difusão limitada eletrônica, e o modelo de dopagem eletroquímico que considera uma dopagem eletroquímica do polímero conjugado, dando a formação de uma junção p-i-n na camada ativa. Usando as medidas de decaimento da corrente sobre uma voltagem aplicada e espectroscopia de impedância /admissão , investigamos o transporte de portadores de carga em um OLEC tendo como camada ativa uma mistura de poli [ ( 9, 9 - dioctyl - 2, 7 - divinileno - fluorenileno ) - alt - co - { 2 - metoxi -5 - ( 2 - etil- hexiloxi ) -1,4 - fenileno } ] ( PFGE ) , com poli ( óxido de etileno ) ( PEO ) complexado com triflato de lítio ( TriLi ) , na proporção 01:01 : X , onde X foi de 0,10 , 0,05 , 0,01 , 0,00. Foram obtidos dados importantes relacionados com efeito iônico e eletrônico durante a operação deste PLEC, sendo que as medidas de transiente e de impedância mostraram que o movimento iônico auxilia o processo de injeção eletrônica. Outro fato relevante é que o desempenho da PLEC é dependente da formação da dupla camada iônica que tem sua espessura abaixo de 10 nm e que o processo de sua formação depende altamente da condução iônica, que por sua vez vai depender da quantidade de íons e de sua mobilidade, sendo influenciando por fatores como concentração de sal e temperatura do dispositivo. As medidas realizadas mostram que as PLECs com 2,5 e 5% de concentração de sal apresentam o melhor desempenho. / Organic Light-emitting Electrochemical Devices (OLECs) belong to a new important branch in organic optoelectronics due to their great potential to be used as dot-pixels for color displays and also to lighting panels. Differently from organic light-emitting diodes (OLEDs), the technology of OLECs is still in early stages of development. In comparison to OLED technology, OLECs have the advantage in being operated in both voltage polarities (forward or reverse bias), and, in addition, their performance is less dependent on the electrode materials and the device thickness. The active layer of an OLEC comprises a mixture of a conjugated electroluminescent polymer and a polymer electrolyte. Consequently, the electrical transport during the device operation involves a combination of ionic and electronic dynamics and intricate effects at the interfaces with the electrodes. The literature presents so far two different approaches to describe the transport phenomenon in the OLECs. The electrodynamic model, which combines ionic charge separation with electronic diffusionlimited process, and the electrochemical doping model that consider an electrochemical doping of the conjugated polymer, giving and the formation of a p-i-n junction in the active layer. Using current decay under an applied voltage measurements and impedance/admittance spectroscopy, we investigate charge carrier transport in an OLEC having as active layer a mixture of poly [(9, 9 - dioctyl - 2, 7 - divinileno - fluorenileno) - alt - co - {2 - methoxy -5 - (2 - ethyl-hexyloxy) -1,4 - phenylene}] (PFGE), with poly (ethylene oxide) (PEO) complexed with lithium triflate (TriLi), in the proportion 1:1:X, where X was 0.10, 0.05, 0.01, 0.00. We have obtained important results related to ionic and electronic effect during this operation PLEC. This measurements of transient current and impedance showed that ionic movement aids the process of electron injection. Another relevant fact is that the performance of PLEC is dependent on the formation of ionic double layer having thickness below 10 nm. The formation of this double layers is highly dependent on the ionic conduction, which in turn will depend on the amount of ions. The ionic mobility is influenced by factors such as salt concentration and temperature of the device. The measurements show that PLECS with 2.5 and 5% salt concentration had the best perform.

The demand for electric vehicles is increasing rapidly as the world is preparing for a fossil fuel-free future in the automotive field. Lithium battery technologies are the most effective options to replace fossil fuels due to their higher energy densities. However, safety remains a major concern in using lithium as the anode, and the development of non-volatile, non-flammable, high conductivity electrolytes is of great importance. In this dissertation, a gel polymer electrolyte (GPE) consisting of ionic liquid, lithium salt, and a polymer has been developed for their application in lithium batteries. A comparative study between GPE and ionic liquid electrolyte (ILE) containing batteries shows a superior cyclic performance up to 5C rate and a better rate capability for 40 cycles for cells with GPE at room temperature. The improvement is attributed to GPE’s improved stability voltage window against lithium as well as higher lithium transference number. The performance of the GPE in lithium-sulfur battery system using sulfur-CNT cathodes shows superior rate capability for the GPE versus ILE for up to 1C rates. Also, GPE containing batteries had higher capacity retention versus ILE when cycled for 500 cycles vii at C/2 rate. Electrochemical impedance spectroscopy (EIS) studies reveal interfacial impedances for ILE containing batteries grew faster than in GPE batteries. The accumulation of insoluble Li2S2/Li2S on the electrodes decreases the active material thus contributes to capacity fading. SEM imaging of cycled cathodes reveals cracks on the surface of cathode recovered from ILE batteries. On the other hand, the improved electrochemical performance of GPE batteries indicates better and more stable passivation layer formation on the surface of the electrodes. Composite GPE (cGPE) containing micro glass fillers were studied to determine their electrochemical performance in Li batteries. GPE with 1 wt% micro fillers show superior rate capability for up to 7C and also cyclic stability for 300 cycles at C/2 rate. In situ, EIS also reveals a rapid increase in charge transfer resistance in GPE batteries, responsible for lowering the capacity during cycling. Improved ion transport properties due to ion-complex formations in the presence of the micro fillers, is evidenced by improved lithium transference number, ionic conduction, and ion-pair dissociation detected using Raman spectroscopy.

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. 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). 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. 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. The methods presented in this thesis serve as a collectedbasis for continued research and development in the area. Keywords: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>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>