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1
Adigoppula, Vinay Kumar. "A study on Nafion® nanocomposite membranes for proton exchange membrane fuel cells." Thesis, Wichita State University, 2011. http://hdl.handle.net/10057/3940.
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With a rise in demand for electricity and depletion of fossil fuel levels, researchers are looking for an alternative resource to generate power, one which is more environmentally friendly. Fuel cells are one of the best alternatives presently available and are considered by many to be the most promising energy sources with efficiencies of up to 60%. Presently, the cost associated with the usage of fuel cells available in the market is quite high. Researchers are trying to bring down costs associated with their usage and improve efficiency. PEM fuel cells are one of the most promising types of fuel cells. Researchers are currently trying to improve its efficiency by improving its electrolyte. Nafion® is one of the main electrolyte used in PEM fuel cells as it acts as proton conductor. Graphene has an exceptionally high surface area to volume ratio and excellent strength. Current research is focused on integrating graphene in PEM fuel cell electrolytes to improve performance. In this study, graphene is added to Nafion® in varying weight percentages to study the performance of the fuel cell given these changes. The graphene weight percentage is varied by 1, 2, 3, and 4. The fuel cell was operated and it was observed that with the addition of graphene there is an improvement in voltage, proton conductivity, and electron conductivity of the PEM fuel cell. The improvement of proton conductivity and electron conductivity followed a linear path with the increase in graphene weight percentage in the Nafion®. Physical properties of the Nafion® membrane with additional graphene were measured and found out that dielectric constant and thermal conductivity also improved linearly with an increase in graphene weight percentage.Thesis (M.S.)--Wichita State University, College of Engineering, Dept. of Mechanical Engineering.
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Coulon, Romain. "Modélisation de la dégradation chimique de membranes dans les piles à combustibles à membrane électrolyte polymère." Phd thesis, Université de Grenoble, 2012. http://tel.archives-ouvertes.fr/tel-00767412.
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Cette thèse propose une approche de modélisation de la dégradation chimique par attaque radicalaire de la membrane dans les piles à combustibles à membrane électrolyte polymère, ainsi que à son impact sur la dégradation de la performance électrochimique. La membrane considérée dans cette étude est de type perfluorosulfonique, avec une structure dépen-dant fortement de son humidification et conditionnant les propriétés de transport. Afin d'étudier la dégradation de la membrane, il faut dans un premier temps établir un modèle de transport, qui sera utilisé aussi bien dans le modèle de dégradation que par les modèles de performance de cellule déjà existants. Une fois ce modèle établi, nous nous focalisons sur la partie dégradation chimique. Après une compréhension globale des phénomènes physico-chimiques se déroulant lors de la dégradation, une mise en équation détaillée est nécessaire. Même les concepts utilisés sont relativement simples, le besoin de nombreux paramètres nous a contraint à simplifier le modèle sur certains points, notamment le mécanisme de dégradation chimique, tant la complexité du phénomène est un frein à la paramétrisa-tion du modèle. Ce modèle, avec ses simplifications et ses hypothèses, est ensuite validé, aussi bien d'un point de vue performance que d'un point de vue dégradation. Il est pour finir exploité dans différents cas de figures, allant de l'utilisation ininterrompue à courant constant (test purement utilisé en laboratoire) à un cyclage plus représentatif de conditions de fonctionnement réelles.
3
Choi, Jonghyun. "Nanofiber Network Composite Membranes for Proton Exchange Membrane Fuel Cells." Case Western Reserve University School of Graduate Studies / OhioLINK, 2010. http://rave.ohiolink.edu/etdc/view?acc_num=case1260461818.
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Sengul, Erce. "Preparation And Performance Of Membrane Electrode Assemblies With Nafion And Alternative Polymer Electrolyte Membranes." Master's thesis, METU, 2007. http://etd.lib.metu.edu.tr/upload/2/12608734/index.pdf.
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Hydrogen and oxygen or air polymer electrolyte membrane fuel cell is one of the most promising electrical energy conversion devices for a sustainable future due to its high efficiency and zero emission. Membrane electrode assembly (MEA), in
which electrochemical reactions occur, is stated to be the heart of the fuel cell. The aim of this study was to develop methods for preparation of MEA with alternative polymer electrolyte membranes and compare their performances with the conventional Nafion®membrane. The alternative membranes were sulphonated polyether-etherketone (SPEEK), composite, blend with sulphonated polyethersulphone (SPES), and polybenzimidazole (PBI). Several powder type MEA preparation techniques were employed by using Nafion®
membrane. These were GDL Spraying, Membrane Spraying, and Decal methods. GDL Spraying and Decal were determined as the most efficient and proper MEA preparation methods. These methods were tried to improve further by changing catalyst loading, introducing pore forming agents, and treating membrane and GDL. The highest performance, which was 0.53 W/cm2, for Nafion®
membrane was obtained at 70 0C cell temperature. In comparison, it was about 0.68 W/cm2 for a commercial MEA at the same temperature. MEA prepared with SPEEK membrane resulted in lower performance. Moreover, it was found that SPEEK membrane was not suitable for high temperature operation. It was stable up to 80 0C under the cell operating conditions. However, with the blend of 10 wt% SPES to SPEEK, the operating temperature was raised up to 90 0C without any membrane deformation. The highest power outputs were 0.29 W/cm2 (at 70 0C) and 0.27 W/cm2 (at 80 0C) for SPEEK and SPEEK-PES blend membrane based MEAs. The highest temperature, which was 150 0C, was attained with PBI based MEA during fuel cell tests.
5
Shi, Jinjun. "Composite Membranes for Proton Exchange Membrane Fuel Cells." Wright State University / OhioLINK, 2008. http://rave.ohiolink.edu/etdc/view?acc_num=wright1214964058.
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Ben, Attia Houssemeddine. "Elaboration et caractérisation des membranes à base de Nafion® / H3 et Nafion® / H1 pour les piles à combustible." Thesis, Grenoble, 2013. http://www.theses.fr/2013GRENI040/document.
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Cette étude concerne l’élaboration et la caractérisation de membranes composites de piles àcombustible PEMFC. Ces nouveaux composites associent un ionomère commercial leNafion® à des charges acides minérales qui sont des acides phosphoantimoniques. Descharges mono et triacides, H1 et H3, ont été utilisées à des taux massiques compris entre 5 et20%. Outre, leur contribution à la conduction protonique et à l’hydratation, les 2 chargesaméliorent sensiblement, même à faible taux, la tenue thermomécanique des membranes. Cerenforcement permet de diminuer l’épaisseur des membranes et donc la chute ohmique. Lestests en pile, réalisés dans une large gamme d’hydratation des gaz et de température,démontrent l’apport incontestable des charges, les membranes composites étant sensiblementplus performantes dès lors que la température de fonctionnement atteint ou dépasse 80°CThis study deals with the elaboration and characterization of composite membranes intendedto be used in PEMFC. These new composites combine a commercial ionomer, Nafion®, withinorganic acidic fillers that are phosphatoantimonic acids. Mono and triacid fillers, H1 and H3, have been used at 5 to 20wt% contents. Besides, their contribution to proton conductionand hydration, both fillers markedly improve, even at low content, the thermomechanicalperformances of the membranes. This reinforcement allows the thickness and, therefore, theohmic drop to be decreased. The MEA tests, performed in a wide range of gas humidificationand temperature, indisputably demonstrate the benefic effect of the fillers; Compositemembranes performing significantly better as soon as the operating temperature reaches orexceed 80°C
7
Aksakal, Ziya Can Şeker Erol. "Hydrogen production from water using solar cells powerd nafion membrane electrolyzers/." [s.l.]: [s.n.], 2007. http://library.iyte.edu.tr/tezlerengelli/master/enerjimuh/T000633.pdf.
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Lavorgna, Marino. "Enhanced sol-gel hybridization of Nafion membrane for fuel cell applications." Thesis, Loughborough University, 2009. https://dspace.lboro.ac.uk/2134/34479.
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Fuel cell technology is one of the emerging energy technologies, both for stationary applications (block power stations) and mobile applications (portable electrical devices). In a standard fuel cell the chemical energy of fuels such as CH3OH or H2 is transformed to electrical energy. High energy efficiency and low emissions make the fuel cell technology attractive compared to traditional combustion engines. The main obstacles to large scale commercialisation of Polymer Exchange Membrane Fuel Cells (PEMFC) are rooted in the proton conducting membrane, which is the most important component of this device. The primary requisites of the hydrated membranes are: (a) high proton conductivity at relatively low humidity levels; (b) low fuel permeability; (c) high chemical, thermal and mechanical stability. Among the different polymeric membranes studied for fuel cell applications only the perfluorosulphonic acid ionomers membranes, such as Nafion®, are actually used commercially.
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Ahmad, Nazir Nadzrinahamin. "Modification and Characterization of Nafion Perfluorinated Ionomer Membrane for Polymer Electrolyte Fuel Cells." University of Akron / OhioLINK, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=akron1310572235.
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Isidoro, Roberta Alvarenga. "Desempenho de membranas híbridas Nafion-TiO2 e eletrocatalisadores de PtSnb/C em células a combustível do tipo PEM alimentadas com etanol e com H2/CO em alta temperatura." Universidade de São Paulo, 2010. http://www.teses.usp.br/teses/disponiveis/85/85134/tde-29082011-160200/.
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Este trabalho teve como objetivo sintetizar eletrólitos híbridos de Nafion-TiO2 e eletrocatalisadores de PtSn/C para a aplicação em células a combustível de oxidação direta de etanol (DEFC) em alta temperatura (130oC). Para tanto, partículas de TiO2 foram incorporadas in-situ em membranas comerciais de Nafion via processo sol-gel. Os materiais resultantes foram caracterizados por análise gravimétrica, absorção de água, DSC, DRX e EDX. Eletrocatalisadores baseados em platina-estanho dispersos em carbono (PtSn/C), de diferentes composições, foram produzidos pelo método de redução por álcool e utilizados como eletrodos anódicos. Os eletrocatalisadores foram caracterizados por DRX, EDX, XPS e MET. A avaliação eletroquímica dos eletrocatalisadores foi realizada por voltametria cíclica, varredura linear anódica de monóxido de carbono (stripping de CO) e cronoamperometria. Ânodos de PtSn/C e cátodos de Pt/C comercial foram dispostos juntamente com os híbridos Nafion-TiO2 para a formação do conjuntos membrana-eletrodos. A avaliação final dos materiais foi realizada por meios de curvas de polarização em células unitárias alimentadas com misturas padrão H2/CO ou etanol no ânodo e com oxigênio no cátodo no intervalo de temperatura de 80 a 130oC. As análises demonstraram que o uso de membranas híbridas diminuiu o crossover de combustível, melhorando o desempenho da célula e que o eletrocatalisador PtSn/C 70:30, produzido pelo método de redução por álcool, foi o que demonstrou melhor desempenho para oxidação de etanol.In this work, Nafion-TiO2 hybrid electrolytes and PtSn/C electrocatalysts were synthesized for the application in direct ethanol fuel cell operating at high temperature (130oC). For this purpose, TiO2 particles were incorporated in commercial Nafion membranes by an in situ sol gel route. The resulting materials were characterized by gravimetric analysis, water uptake, DSC, XRD and EDX. Electrocatalysts based on carbon dispersed platinum-tin (PtSn/C), with different composition, were produced by alcohol-reduction method and were employed as anodic electrode. The electrocatalysts were characterized by XRD, EDX, XPS and transmission electronic spectroscopy. The electrochemical characterization was conducted by cyclic voltametry, carbon monoxide linear anodic voltammetry (CO stripping), and chronoamperometry. Membrane-electrodes assembly (MEAs) were formed with PtSn/C anodes, Pt/C cathodes and Nafion-TiO2 hybrids. The performance of these MEA was evaluated in single-cell fed with H2/CO mixture or ethanol solution at the anode and oxygen at the cathode in the temperature range of 80-130oC. The analysis showed that the hybrid membranes improved the DEFC performance due to crossover suppression and that PtSn/C 70:30 electrocatalysts, prepared by an alcohol reduction process, showed better performance in ethanol oxidation.
11
Agarwal, Rohit. "Preparation and Characterisation of Stabilized Nafion/Phosphotungstic Acid Composite Membranes for Proton Exchange Membrane Fuel Cell (PEMFC) Automobile Engines." Master's thesis, University of Central Florida, 2008. http://digital.library.ucf.edu/cdm/ref/collection/ETD/id/4236.
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Membrane durability is one of the limiting factors for proton exchange membrane fuel cell (PEMFC) commercialisation by limiting the lifetime of the membrane via electrochemical / mechanical / thermal degradation. Lower internal humidity in the membrane at high temperature (>100 oC) and low relative humidity (25-50 %RH) operating conditions leads to increased resistance, lowering of performance and higher degradation rate. One of the promising candidates is composite proton exchange membranes (CPEMs) which have heteropoly acid (HPA) e.g. Phosphotungstic acid (PTA) doped throughout the Nafion® matrix. HPA is primarily responsible for carrying intrinsic water which reduces the external water dependence. The role of relative humidity during membrane casting was studied using surface analysis tools such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Thermo-gravimetric analysis (TGA), and Scanning electron microscopy (SEM) / Energy dispersive spectrometer (EDS). Membrane casting at lower relative humidity (30% approx.) results in finer size, and better PTA incorporation in the composite membrane. The effect of increase in PTA concentration in the Nafion matrix was studied with regards to conductivity, performance and durability. In-plane conductivity measurements were performed at 80 oC and 120 oC. During theses measurements, relative humidity was varied from 20% to 100% RH. Membrane conductivity invariably increases on increasing the relative humidity or operating temperature of the cell. Membrane conductivity increases with increasing PTA content from 3% to 25% PTA but never reaches the conductivity of membrane with 0% PTA. Possible explanation might be the role of cesium in PTA stabilisation process. Cesium forms a complex compound with PTA inside host matrix, rendering the PTA incapable of holding water. In plane conductivity measurements only measure surface conductivity, hence another reason might be the existence of a PTA skin on the membrane surface which is not truly representative of the whole membrane. XRD revealed that the structure of the composite membrane changes significantly on addition of PTA. Membrane with 3% PTA has structure similar to Nafion® and does not exhibit the characteristic 25o and 35o 2Ө peaks while membrane with 15% PTA and 25% PTA have strong characteristic PTA peaks. Also the membrane structure with 25% PTA matches well with that of PTA.6H2O. By applying the Scherer formula, PTA particle size was calculated from Full width half maximum (FWHM) studies at 17o 2Ө peak of the membranes. Particles coalesce on increasing the PTA concentration in the membrane leading to larger particles but still all particles were in nanometer range. Also the FWHM of membranes decreased at 17o 2Ө peak on increasing the PTA concentration, leading to higher crystallinity in the membrane. Structure analysis by FTIR indicated increase in PTA signature intensity dips, as the PTA concentration in membrane increases from 0-25%. Also by FTIR studies, it was found that some PTA is lost during the processing step as shown by comparison of as cast and protonated spectra. Possible reasoning might be that some amount of PTA does not gets cesium stabilized which gets leached away during processing. TGA studies were performed which showed no signs of early thermal degradation (temperature >300 oC); hence the assumption that all membranes are thermally robust for intended fuel cell applications. The membranes with different amounts of PTA were then catalyst coated and tested for 100-hour at open circuit voltage (OCV), 30% RH and 90 oC. By increasing the PTA in the host Nafion® matrix, the percent change in fuel crossover decreases, percent change in ECA increases, cathode fluoride emission rate decreases, and percent change in OCV decreases after the 100 hour test. Possible reasons for decreasing percentage of fuel crossover might be the increased internal humidity of the membrane due to increasing PTA incorporation. It is reported that during higher relative humidity operation, there is decrease in fuel crossover rate. Increasing ECA percentage loss might be due to the fact that HPA in the membrane can get adsorbed on the catalyst sites, rendering the sites inactive for redox reaction. Decrease in cathode fluorine emission rate (FER) might be due to the fact that there is more water available internally in the membrane as compared to Nafion®. It is reported that at higher relative humidity, FER decreases. ECA and crossover both contribute to the OCV losses. Higher component of OCV is crossover loss, which results in mixed potentials. Hence decreasing percentage of crossover might be the reason behind the decreasing OCV loss. Initial performance of fuel cell increases with increasing PTA concentration, but after the 100 hour test, higher PTA membrane exhibited highest performance loss. Increasing initial fuel cell performance can be due to the lowering of resistance due to PTA addition. Increasing ECA losses might be responsible for the increasing performance losses on adding more PTA to host membrane.M.S.
Department of Mechanical, Materials and Aerospace Engineering;
Engineering and Computer Science
Materials Science & Engr MSMSE
12
Balogun, Emmanuel O. "Comparative analysis of Polymer Electrolyte Membrane (PEM) fuel cells." Master's thesis, University of Cape Town, 2018. http://hdl.handle.net/11427/29764.
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Per-Fluoro-Sulphonic-Acid (PFSA) ionomers have been singled out as the preferable ionomers for making the Polymer Electrolyte Membrane Fuel Cells (PEMFC) membranes owing to their extensive intrinsic chemical stability and super sulfonic acid strength which is core to the PEMFC proton conductivity. This thesis presents a deeper analysis into these PFSA ionomer membrane electrode assemblies (MEA), presenting an electrochemical-analytical comparative analysis of the two basic types, which are the Long-Side-Chain (LSC) Nafion® and the ShortSide-Chain (SSC) Aquivion® ionomer MEA with emphasis on performance and durability which are currently not well understood. In particular, electrochemical circuit models and semiempirical models were employed to enable distinguishable comparative analysis. Also, in this thesis, we present a further probe into the effect of ionomer ink making processes, critically investigating the effect of the High Share Dispersion (HSD) process on both the Nafion® and Aquivion® ionomer membrane electrode assembly (MEA). The findings in this research provides a valuable insight into the performance and durability of PFSA ionomer membrane under various application criteria. The effect of operating parameters and accelerated stress testing (AST) on the PFSA ionomers was determined using electrochemical impedance spectroscopy (EIS) and electronic circuit model (ECM) analysis. The result of this study, shows that the ionomer ink making process for Nafion® and Aquivion® MEAs are not transferrable. Analysis of the PEMFC performance upon application of the high shear dispersion (HSD) process showed that Nafion® MEA had a 10.47% increase in voltage while the Aquivion® MEA had a 2.53% decrease in voltage at current density of 1.14A/cm2 . Also, upon accelerated stress testing, the Nafion® showed a 10.49% increase in its voltage while the Aquivion® on the other hand had a 7.16% decrease in voltage at 0.66A/cm2 . Thus indicating the HSD process enhances the performance of the Nafion® MEA and inhibits the performance of the Aquivion® MEA.
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Marchand, Gabriel. "Advanced Computer Simulations of Nafion / Water Systems." Thesis, Bordeaux 1, 2012. http://www.theses.fr/2012BOR14553/document.
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Les membranes fluorées sont utilisées en particulier dans les dénommées piles à combustible à membrane électrolyte polymère. Grâce à sa grande mobilité en protons, le célèbre ionomer Nafion® (Dupont) est un matériau de référence pour les applications liées aux piles à combustible. En présence d’eau ou d’autres solvants hydrophiles la membrane se sépare en une matrice polymérique hydrophobe et une sous-phase aqueuse contenant des clusters d’eau et ions, dont les tailles et la connectivité augmente quand la quantité d’eau augmente [1]. Quelle est la morphologie du Nafion et la structure du solvant, dans de tels systèmes?Il a été récemment montré [2] sur des simulations de large systèmes que plusieurs modèles morphologiques reproduisent les données expérimentales de diffusion, évoquant l’incapacité des mesures de diffusion seules à élucider la véritable structure du Nafion.Néanmoins, un modèle ’aléatoire’ décrit dans [2], c’est à dire l’unique modèle étudié sans présumer d’une structure initiale particulière, n’a pas pu reproduire les données expérimentales.Générer en simulations moléculaires des configurations du système qui soient vraiment décorrélées de la configuration initiale reste un vrai défi statistique. Les échelles de temps réalisables ne permettent simplement pas d’obtenir des mouvements significatifs du polymère (comme des transitions de conformations, repliements de chaînes, etc.). Nous proposons ainsi dans cette étude un nouveau modèle de Nafion à morphologie aléatoire. Un algorithme récemment développé est utilisée pour générer des chaînes de Nafion avec des chemins et des points de départ aléatoires. Une différence majeure avec le modèle aléatoire dans [2] est que nous ne construisons pas nos systèmes à une densité proche de la densité finale. Pour ne pas démarrer avec des chaînes trop enchevêtrées, les systèmes sont initialement préparés à une densité en dessous de la référence expérimentale. La densité après équilibration est de nouveau proche de l’expérience. Bien qu’il soit facilement envisageable d’améliorer les nouveaux algorithmes, nous démontrons ici qu’avec la présente version plusieurs séries de configurations compatibles avec les données expérimentales de diffusion disponibles peuvent être générées et équilibrées. Douze large systèmes de Nafion à morphologie aléatoire sont construits avec des positions initiales des atomes ainsi que des quantités d’eau et des longueurs de chaînes (Nafion/Hyflon) différentes. Ils sont équilibrés puis simulés sur plusieurs dizaines de nanosecondes. Après équilibration, les structures sont, comme indiqué ci-dessus,compatibles avec les données expérimentales de diffusion. En plus nous étudions un modèle ressemblant à celui de Schmidt-Rohr and Chen [3], c’est à-dire le plus récent modèle morphologique. Avec ce modèle, les données expérimentales sont également reproduites de manière satisfaisante, d’où la prolongation du débat sur la structure du Nafion. La cohésion entre les valeurs calculées et celles mesurées expérimentalement incite à des analyses plus en détails de ces configurations obtenues. Nous caractérisons et analysons les structures locales, intermédiaires et à grande échelle avec divers paramètres structuraux et distributions des tailles de domaines. Nous calculons donc, par exemple, des fonctions de distribution radiale (rdf), des facteurs de structure (S(q)) totaux et partiels tout comme des nombres et des tailles de clusters hydrophiles (selon la définition d’un cluster). La dynamique de diverses espèces dans le système est également examinée,par exemple au travers des déplacements carrés moyens (msd) et des coefficients de diffusion. Ces simulations sont probablement à la limite de ce qui est réalisable aujourd’hui avec des simulations ’full-atom’ du type MD. Nous espérons que ce travail fera avancer le débat sur la structure et la dynamique de ces matériaux importantsPerfluorinated membranes are used in particular in polymer electrolyte fuel cells(PEFC). The well-known ionomer Nafion® (Dupont) is, due to its high proton mobility,a reference material for fuel cell applications. In water or other hydrophilic solvents themembrane segregates into a hydrophobic backbone matrix and a hydrophilic sub-phasecontaining clusters of both water and ions, where the cluster sizes and connectivity increasewith increasing water content [1].What is the Nafion morphology and the structure of the solvent in such systems? It hasbeen shown recently [2] on large simulated systems that several morphological modelsfit the experimental scattering data, suggesting the inability of scattering experimentsalone to elucidate the true structure of Nafion. However, a ’random’ model describedin [2], i.e. the only explored model that did not assume a particular initial structure,could not reproduce the experimental data.It remains a real computational challenge to generate in molecular simulations systemconfigurations which are really decorrelated from the initial one. The time scales thatcan be achieved simply do not allow to obtain significant motions of the polymer (e.g.conformational changes, folding, etc.). We thus propose in this work a new randommodel of Nafion. A newly developped algorithm is used to generate Nafion chains withrandom growth paths and random starting points. A significant difference with therandom model in [2] is that we do not build our systems at a density close to the finalone. In order not to start with too much entangled chains, the systems are initiallybuilt at a density below the experimental one. The density after equilibration is againclose to the experimental one.Even though further improvements of the new algorithms can easily be envisaged,we demonstrate here that with the present version several sets of configurations thatare compatible with the available scattering data can be generated and equilibrated.Twelve large random Nafion systems are built with different initial positions of theatoms as well as different water contents and side chain lengths (Nafion/Hyflon). Theyare equilibrated and then simulated for several ten nanoseconds. After equilibration,the structures are, as mentioned, compatible with the experimental scattering data. Inaddition we study a model similar to the one by Schmidt-Rohr and Chen [3], i.e. thenewest morphological model of Nafion. The experimental scattering data are also satisfactorilyreproduced with this model, hence, the prolonged debate over the structureof Nafion.This agreement gives confidence that a more detailed analysis of the so-obtained configurationsis scientifically warranted. We characterize and analyze the local, intermediateand large-scale structures by various structural parameters and domain size distributions.We therefore compute, for example, radial distribution functions (rdf), total andpartial structure factors (S(q)) as well as numbers and sizes of hydrophilic clusters (dependingon the definition of a cluster). The dynamics of various species in the systemis also investigated, e.g. via the computation of the mean square displacements (msd)and the self-diffusion coefficients. These simulations are probably at the limit of whatcan today be achieved with all-atom molecular simulations of the MD type. We hopethat this work will advance the ongoing debate on the structure and dynamics of theseimportant materials
Perfluorierte Membranen werden insbesondere in Polymerelectrolyt-Brennstoffzellen(PEFC) eingesetzt. Das wohlbekannte Ionomer Nafion® (Dupont) ist wegen seinerhohen Protonenbeweglichkeit ein Referenzmaterial für solche Anwendungen in Brennstoffzellen.Die Membran separiert in Wasser oder anderen hydrophilen Lösungsmittelin eine hydrophobe Polymermatrix und eine hydrophile Subphase, die Cluster mitWasser und Ionen enthält. Dabei vergroeßern sich die Ausdehnung der Cluster und ihreKonnektivität mit zunehmendem Wassergehalt [1].Welche ist die Morphologie des Nafions und die Struktur des Lösungsmittels in diesenSystemen? Es ist jüngst anhand großer simulierter Systeme gezeigt worden [2], dassmehrere morphologische Modelle die experimentellen Streudaten wiedergeben können,was nahelegt, dass solche Streudaten alleine nicht geeignet sind, die wahre Strukturdes Nafion aufzudecken. Ein in [2] beschriebenes ’Zufallsmodell’, d.h. das einzigeder untersuchten Modelle, das keine besondere Anfangsstruktur annahm, konnte dieexperimentellen Daten allerdings nicht wiedergeben.In molekularen Computersimulationen Konfigurationen zu erzeugen, die wirklich nichtmehr mit der angenommenen Anfangskonfiguration korreliert sind, bleibt eine echteHerausforderung. Die erreichbaren Zeitskalen sind zu kurz, um eine signifikante Bewegungdes Polymers (z.B Konformationsänderungen, Faltungen, usw.) zuzulassen. Indieser Arbeit wird daher ein neues Zufallsmodell für Nafion vorgestellt. Ein neuentwickelterAlgorithmus erzeugt Nafionketten mit zufälligem Wachstumspfad ausgehendvon zufälligen Anfangspunkten. Ein signifikanter Unterschied zu dem Zufallsmodellvon [2] ist, dass hier nicht versucht wird, die Systeme bei einer Dichte vergleichbarder experimentellen Dichte aufzubauen. Anstattdessen werden die Systeme, um alzustarkes Verknäuelung zu vermeiden, anfangs bei einer deutlich kleineren Dichte erzeugt.Nach äquilibrierung ist die Systemdichte wieder in etwa gleich der experimentellen.Wiewohl weitere Verbesserungen des neu Algorithmuses leicht ins Auge gefaßt werdenkönnen, so kann hier doch gezeigt werden, dass mit der gegenwärtigen VersionKonfigurationen erzeugt und äquilibriert werden können, die mit den verfügbarenStreudaten kompatibel sind. Zwölf große Nafion Zufallssysteme, mit verschiedenenAnfangspositionen der Atome, verschiedenem Wassergehalt und Längen der Seitenketten(Nafion/Hyflon) werden aufgebaut. Diese werden äquilibriert und mehrerezehn Nanosekunden lang simuliert. Nach der äquilibrierung sind die Strukturen, wieerwähnt, kompatibel mit den experimentellen Streudaten. Weiterhin wird ein Modellähnlich dem von Schmidt-Rohr und Chen [3], d.h. dem neuesten morphologischen Modellfür Nafion, studiert. Auch hier werden die experimentellen Streudaten zufriedenstellendwiedergegeben, daher die weiterhin bestehende Debatte über die Struktur desNafion.Die gefundenen übereinstimmungen lassen darauf vertrauen, dass eine detaillierte Analyseder simulierten Konfigurationen wissenschaftlich sinnvoll ist. So wird die Strukturder Systeme auf verschiedenen Längenskalen charakterisiert, zum Beispiel durch radialePaarverteilungsfunktionen (rdf), totale und partielle Strukturfaktoren (S(q)) sowieAnzahl- und Größenverteilungen hydrophiler Cluster (abhängig von der Definition einesClusters). Die Dynamik einzelner Spezies im System wird ebenfalls untersucht, zumBeispiel durch die Berechnung der mittleren quadratischen Verschiebungen (msd) undder Selbstdiffusionskoeffizienten. Diese Simulationen sind wahrscheinlich an der Grenzedessen, was heute mit ’all-atom’ molekularen MD-Simulationen möglich ist. Ich vertrauedarauf, dass diese Arbeit dennoch einen Fortschritt in der aktuellen Debatte überdie Struktur und Dynamik dieser wichtigen Materiale darstellt
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Klose, Carolin, Matthias Breitwieser, Severin Vierrath, Matthias Klingele, Hyeongrae Cho, Andreas Büchler, Jochen Kerres, and Simon Thiele. "Electrospun sulfonated poly(ether ketone) nanofibers as proton conductive reinforcement for durable Nafion composite membranes." Elsevier, 2017. https://publish.fid-move.qucosa.de/id/qucosa%3A72523.
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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.
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Hlabano-Moyo, Bongibethu Msekeli. "Separation of SO2/O2 using membrane technology / Bongibethu Msekeli Hlabano-Moyo." Thesis, North-West University, 2013. http://hdl.handle.net/10394/9447.
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The Hybrid Sulphur process is one technology out of a multitude of known technologies responsible for hydrogen production. Within the latter hydrogen production cycle, it is pivotal to recover O2 as a by-product from a sulphuric acid decomposition reaction that produces SO2, H2O and O2. It is assumed that a simple phase separation stage carried out on the reaction products would liberate SO2 and O2 as a gaseous mixture leaving behind H2O in the liquid state.
Several separation technologies are available to effect SO2/O2 separation, but membrane technology has proved to be dearer due to simplicity of the technology, low capital and energy costs. It is a pity though that insignificant work has been done that considers the SO2/O2 binary system in the membrane technology context. Of the insignificant work done, non – commercial membranes were employed. It is on the latter background that the present study was proposed.
Six commercial membranes were selected from literature, two (Udel Polysulfone and Teflon AF 2400) of which are currently used in gas separation applications and the remainder (Hyflon M, Hyflon F, Halar and Nafion 117) not necessarily used as gas separation membranes but present a potential of separating SO2/O2. The inclusion of the latter four membranes sought to unearth unknown gas separation potentials of the membranes based on hypothetical 1 μm thick membranes.
A screening technique was employed to eliminate poor performing membranes through pure component permeation of SO2, O2, N2 and CO2. The use of the additional gases (N2 and CO2) was meant to allow the generation of a pool of data that would be used as a yardstick to compare to literature and thus validate the authenticity of the designed set up. The single permeation experiments were carried out at 25°C and at absolute gas feed pressures of 1 bar, 2 bar and 3 bar, with the exception of Hyflon F experiments that were carried out at 3.85 bar, 2.85 bar and 1.85 bar also at 25°C. The effect of pressure on gas permeability and ideal selectivity of all gases against O2 was investigated. Udel Polysulfone and Nafion 117 presented clearly evident pressure dependant SO2 permeabilities whilst CO2, N2 and O2 permeabilities were sluggishly dependant on pressure in all membranes. Gas flux in general increased with increasing pressure as pressure is essentially the driving force for permeability. Membrane screening for further investigation was then performed based on a compromise between SO2/O2 ideal selectivity and SO2 flux in hypothetical 1 μm thick membranes. Membranes that presented the best SO2/O2 selectivity include, Udel Polysulfone with SO2/O2 selectivities of 46, 58 and 314 at 1 bar, 2 bar and 3 bar respectively, Nafion 117 with SO2/O2 selectivities of 30, 35 and 40 at 1 bar, 2 bar and 3 bar respectively and Halar with a SO2/O2 selectivity of 17 at 3 bar. The best SO2 flux through hypothetical 1 μm thick membranes was manifested in Teflon AF 2400 with SO2 fluxes of 3.6 m3.m-2.hr-1, 5.9 m3.m-2.hr-1 and 9.9 m3.m-2.hr-1 at trans-membrane pressures of 1 bar, 2 Bar and 3 Bar respectively, Udel Polysulfone with SO2 fluxes of 0.13 m3.m-2.hr-1, 0.32 m3.m-2.hr-1 and 2.56 m3.m-2.hr-1 at trans-membrane pressures of 1 bar, 2 bar and 3 bar respectively and Nafion 117 with SO2 fluxes of 0.48 m3.m-2.hr-1, 1.03 m3.m-2.hr-1 and 1.79 m3.m-2.hr-1 at 1 bar, 2 bar and 3 bar trans-membrane pressures respectively. Despite Teflon AF 2400 presenting the highest SO2 flux, the poor SO2/O2 ideal selectivity ≈ 1 rendered the membrane unfit for further investigation. The low SO2 flux (0.02 m3.m-2.hr-1) presented by Halar also rendered the membrane unfit for further investigation despite the relatively fair SO2/O2 ideal selectivity of 17.
Binary permeation experiments were then performed on Udel Polysulfone and Nafion 117 after passing the single permeation screening test. Gas mixture compositions of (25 wt %:75 wt %, SO2:O2), (50 wt %:50 wt %, SO2:O2) and (75 wt %:25 wt %, SO2:O2) were employed. The binary permeation experiments were carried out at a temperature range of 15°C to 55°C and a SO2 feed partial pressure range of 1.1 ± 0.1 bar to 2.3 ± 0.1 bar.
The SO2 permeate composition increased with pressure and decreased with temperature in both Udel Polysulfone and Nafion 117. Udel Polysulfone presented a superior SO2/O2 separation potential, concentrating a (25 wt %:75 wt %, SO2:O2) gas mixture to (94 wt %:6 wt %, SO2:O2) in a single step at 15°C and 2.2 ± 0.1 bar SO2 feed partial pressure. Nafion 117 concentrated the same gas mixture to (87 wt %:13 wt %, SO2:O2) also in a single step at 15 °C and 2.4 ± 0.1 bar SO2 feed partial pressure. Based on hypothetical 1 μm thick membranes, Nafion 117 presented generally high SO2 molar fluxes in mixture with O2 of about a magnitude higher than the SO2 molar fluxes presented in Udel Polysulfone. Also, Nafion 117 proved to be less prone to plasticisation within the pressure range considered. Despite Udel Polysulfone presenting generally lower SO2 molar fluxes, Udel Polysulfone was deemed to be the ideal membrane for the current SO2/O2 separation application as thicknesses of 1 μm of Nafion the perfluorosulfonic acid based membrane are currently unknown and also Udel Polysulfone presented the best SO2/O2 separation capability. The latter findings are envisaged to prompt further research on the production of ultra-thin perfluoro-sulfonic acid based membranes for the current application.Thesis (MIng (Chemical Engineering))--North-West University, Potchefstroom Campus, 2013
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Dresch, Mauro André. "Síntese e caracterizção eletroquímica de membranas híbridas Nafion-SIO2 para a aplicação como eletrólito polimérico em células a combustível tipo PEM." Universidade de São Paulo, 2009. http://www.teses.usp.br/teses/disponiveis/85/85134/tde-26092011-141218/.
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Neste trabalho foi estudado o efeito dos parâmetros de síntese na resposta de polarização de híbridos Nafion-SiO2 como eletrólitos em células a combustível poliméricas (PEMFC) em elevadas temperaturas (até 130 °C). A fase inorgânica foi adicionada à matriz polimérica com o objetivo de aumentar a retenção de água na membrana em elevadas temperaturas (acima de 100 °C); melhorar as propriedades mecânicas do Nafion e favorecer cineticamente as reações eletródicas. As membranas foram preparadas a partir da incorporação in-situ de sílica em membranas comerciais de Nafion por rota sol-gel acompanhada de catálise ácida. Os parâmetros de síntese, tais como: concentração do catalisador ácido, natureza do solvente, temperatura e tempo de reação e concentração do precursor de silício (Tetraetil-Ortosilicato TEOS) foram avaliados em função do grau de incorporação e resposta de polarização. Os híbridos Nafion-SiO2 foram física e quimicamente caracterizados por gravimetria, termogravimetria (TG), microscopia eletrônica de varredura e espectroscopia de energia dispersiva de raios X (MEV-EDX), espectroscopia de impedância eletroquímica (EIS) e espalhamento de raios X em baixos ângulos (SAXS). Por fim, os híbridos sintetizados foram avaliados diretamente como eletrólitos em células PEM unitárias alimentadas com hidrogênio (H2) e oxigênio (O2) no intervalo de temperatura de 80 ºC a 130 ºC e a 130 ºC em condições de umidade relativa reduzida (75 e 50%). Resumidamente, o desempenho dos híbridos se mostrou fortemente dependente dos parâmetros de síntese, principalmente, o tipo de álcool utilizado e concentração inicial de TEOS.In this work, the effect of sol-gel synthesis parameters on the preparation and polarization response of Nafion-SiO2 hybrids as electrolytes for proton exchange membrane fuel cells (PEMFC) operating at high temperatures (130 oC) was evaluated. The inorganic phase was incorporated in a Nafion matrix with the following purposes: to improve the Nafion water uptake at high temperatures (> 100 oC); to increase the mechanical strength of Nafion and; to accelerate the electrode reactions. The hybrids were prepared by an in-situ incorporation of silica into commercial Nafion membranes using an acid-catalyzed sol-gel route. The effects of synthesis parameters, such as catalyst concentration, sol-gel solvent, temperature and time of both hydrolysis and condensation reactions, and silicon precursor concentration (Tetraethylorthosilicate TEOS), were evaluated as a function on the incorporation degree and polarization response. Nafion-SiO2 hybrids were characterized by gravimetry, thermogravimetric analysis (TGA), scanning electron microscopy and X-ray dispersive energy (SEM-EDS), electrochemical impedance spectroscopy (EIS), and X-ray small angle scattering (SAXS). The hybrids were tested as electrolyte in single H2/O2 fuel cells in the temperature range of 80 130 oC and at 130 oC and reduced relative humidity (75% and 50%). Summarily, the hybrid performance showed to be strongly dependent on the synthesis parameters, mainly, the type of alcohol and the TEOS concentration.
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Chan, Wai-hung, and 陳偉雄. "Fabrication of aligned carbon nanotubes layer and interfacing with Nafion membrane for potential application in fuel cells." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2009. http://hub.hku.hk/bib/B44518559.
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Thomas, Michel. "Transport de l'eau à travers une membrane perfluorosulfonique Nafion : relations avec la microstructure : développement de membranes composites à haute perméabilité aux gaz." Lyon 1, 1989. http://www.theses.fr/1989LYO10174.
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Les problemes de separation gazeuse sont actuellement au premier plan des preoccupations industrielles avec en particulier le sechage, la desacification et la deshydrogenation des gaz petroliers. La demarche scientifique fixee pour cette etude consiste a preciser les relations entre les parametres du tranport et la structure microscopique du polymere. La membrane perfluorosulfonique nafion et l'eau ont ete retenues comme systeme de depart. Nous avons developpe quatre types de mesure: i) mesure des coefficients dlu transport (permeabilite, diffusion, solubilite); ii) mesure des coefficients de self-diffusion en phase vapeur par utilisation de molecules marquees; iii) mesure directe des profils de concentration par diffusion de neutrons aux petits angles; iiii) mesure des parametres du transport hydraulique et osmotique. Pour les fractions volumiques en eau inferieures a 18% la diffusion a lieu dans un milieu multiphasqiue avec dispersion des zones ioniques hydratees diffusives dans la matrice organique. Le transport est regi par les processus superficiels et la relaxation du polymere. Pour les fractions volumiques en eau superieures a 18 % la percolation des clusters assure la realisation d'une phase continue diffusive. Dans ce cas, la relaxation du polymere est rapide et n'intervient pas sur la diffusion
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Otmani, Nassim. "Détermination des contraintes mécaniques dans les membranes Nafion® au cours du fonctionnement en pile à combustible." Grenoble INPG, 2009. http://www.theses.fr/2009INPG0117.
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La durabilité des piles à combustible de type PEMFC n’est pas suffisante pour être compatible avec les applications visées. Cette thèse propose de déterminer les contraintes mécaniques subies par les membranes Nafion® dans la PEMFC. Dans un premier temps, les propriétés élastoplastiques ont été mesurées sur la gamme de températures et d’humidités relatives de fonctionnement de la pile. Dans ces mêmes conditions, le gonflement de la membrane a aussi été examiné. Un lien entre structure, quantité d’eau et contraintes mécaniques du Nafion® a pu être mis en évidence. Ces propriétés ont ensuite été incorporées dans un modèle construit pour décrire le comportement mécanique de la PEMFC. Après avoir été validé expérimentalement, ce modèle a été utilisé pour simuler des chargements hygrothermiques représentatifs du fonctionnement réel de la PEMFC. Une étude paramétrique a permis d’émettre des recommandations sur les pratiques à adopter pour minimiser les contraintes dans la membraneThe durability of proton exchange membrane fuel cells is still not sufficient to be compatible with large-scale applications. The work of this PhD aims at determining the mechanical streses endured by the Nafion® membranes during the PEMFC operation. The elastoplastic properties of Nafion® have been measured in the PEMFC hygrothermal conditions, thanks to tensile tests. In the same conditions, the swelling has been investigated. A link between structure, water content, swelling and mechanical stresses has also highlighted. These properties have then been incorporated in a model built to describe the PEMFC mechanical behaviour. After an experimental validation, this model has been used to simulate hygrothermal loadings representative of the real-life PEMFC operation. A parametric study has given the possibility to advocate some technical advises in order to minimize the mechanical stresses within the membrane
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Schmidt, Stephanie Ann. "Mathematical models of ion transport through nafion membranes in modified electrodes and fuel cells without electroneutrality." Diss., University of Iowa, 2010. https://ir.uiowa.edu/etd/734.
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Electrodes are modified with polymer films to grant novel permeability. Often, redox probes partition from solution into film and are electrolyzed at the electrode. This creates a flux of probe into the polymer film and a flux of electrolyzed probe out of the polymer film. Transport of the probe through the film is governed by diffusion and migration, mathematically described from the Nernst-Planck equation as J_{i}=-D_{i}((∂C_{i}(x,t))/(∂x))-((z_{i}F)/(RT))D_{i}C_{i}(x,t)((∂Φ(x,t))/(∂x)) where x is the distance from the electrode, t is time, C_{i}(x,t) is space and time dependant concentration of the probe i, z_{i} is the charge of the probe i, F is Faraday's constant, R is the gas constant, T is absolute temperature, J_{i} is the flux of the probe i, D_{i} is the diffusion constant of the probe i and Φ(x,t) is the space and time dependant potential.
In most natural systems, charge accumulation is not appreciably noticed, the system behaves in such a way that a charged ion is neutralized by a counterion. This is called electroneutrality and is mathematically represented by Laplace's condition on the potential, ((∂²Φ)/(∂x²))=0. In some systems, it is not clear if counterions are readily available to neutralize an ion. In such a system, there may not be electroneutrality, giving Poisson's equation to replace Laplace's condition as ((∂²Φ)/(∂x²))=-(F/ɛ)∑_{i}z_{i}C_{i}(x,t) where ɛ is the relative permittivity. The addition of Poisson's condition makes the system nonsolvable. In addition, the magnitude of F/ɛ creates difficulty simulating the system using standard techniques. The first system investigated determines the concentration and potential profiles over the polymer membrane of a fuel cell without electroneutrality.
In some systems, the probes can not easily diffuse around each other, certain polymer film environments prevent such a swap of location as diffusion is commonly thought to occur. A more generalized form of the Nernst-Planck equation describes spatially varying diffusion coefficient as J=-D(x,t)((∂C(x,t))/(∂x))-((zF)/(RT))D(x,t)C(x,t)((∂Φ(x,t))/(∂x)). D(x,t) is space and time dependent diffusion, usually thought of with a physical diffusion term and an ion hopping term. The second system this thesis investigates is a modified electrode system where electron hopping is responsible for a majority of the probe transport within the film.
Lastly, the beginnings of a method are presented to easily determine the physical diffusion rate of a probe within a modified electrode system based on known system parameters.
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Bi, Xuanxuan. "Investigating the factors for the low cycle life of sodium oxygen batteries." The Ohio State University, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=osu1419690198.
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Sephane, Nicolas. "Elaboration d'électrodes de piles à combustible à membrane par un procédé de transfert de couches catalytiques." Thesis, Montpellier 2, 2013. http://www.theses.fr/2013MON20185.
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Ces travaux de thèse portent sur l'optimisation des méthodes de fabrication des assemblages membrane électrodes des Piles à Membrane Echangeuse de Protons (PEMFC, Proton Exchange Membrane Fuel Cell). Ils ont pour objectif d'optimiser le dépôt des couches catalytiques sur la membrane par une méthode de transfert. Le procédé a été utilisé pour fabriquer d'une part des assemblages à membrane Nafion® pour les piles à combustible à membrane fonctionnant à 80 °C (PEMFC) et d'autre part des assemblages à membrane polybenzimidazole dopée en acide phosphorique pour les PEMFC à haute température (160 °C). Au cours de cette étude, la détermination précise de la quantité de platine a été rendue possible par des mesures non destructives en fluorescence X. Nous avons développé également une méthode originale de fabrication de suspensions de blendes Nafion-PBI qui ont été incorporées dans les électrodes des assemblages à membrane PBI. L'effet de la composition, des épaisseurs et du mode de préparation des électrodes sur les performances des assemblages a été discuté. Les assemblages membrane électrodes à membrane PBI ont été caractérisés par des mesures en polarisation et en spectroscopie d'impédance (EIS). La détermination de surface active d'électrode a été réalisée par des mesures en voltammétrie cyclique in-situ (CV). La mise au point du procédé de fabrication des électrodes par transfert de couches actives sur membrane a permis d'obtenir des informations importantes sur les conditions de préparation des électrodes. Les performances des assemblages à membrane Nafion® sont supérieures à celles obtenues sur des assemblages de référence avec des électrodes supportées sur couche de diffusion (GDE). Il a été possible de réaliser pour la première fois des assemblages avec un dépôt sur des membranes polybenzimidazole déjà dopées en acide, les premiers résultats obtenus sont extrêmement encourageants. Le procédé de transfert des couches catalytiques pourrait être adapté pour réaliser des dépôts sur d'autres variétés de membranes dopées ou non dopées en acideThis work concerns the optimization of the fabrication processes of membrane electrode assemblies for the Proton Exchange Membrane Fuel Cell (PEMFC). The objective is to carry out the deposition of catalyst layers onto the membranes by a transfer process. The optimization of the catalyst layer compositions and its morphology is crucial for this process. Assemblies with Nafion® membranes for PEMFC working at 80 °C and phosphoric acid doped polybenzimidazole membranes for HTPEMFC (160 °C) have been prepared by this method. X-ray fluorescence spectrometry, due to its non destructive nature, was applied for precise analysis of platinum loading on the electrodes. In this work, a new method was also developed for the preparation of Nafion-PBI blend suspensions that have been incorporated in the electrodes of the PBI membrane electrodes assemblies. The PBI membrane electrode assemblies have been characterized by polarization measurements and electrochemical impedance spectroscopy (EIS). The in situ PEM Fuel Cell electrochemical surface area (ECSA) has been determined by cyclic voltammétrie measurements. The performances of Nafion membrane assemblies are higher than those obtained on reference assemblies, with gas diffusion layer supported electrodes. Promising results have been obtained on the assemblies performed for the first time with acid doped PBI membranes. The transfer process of the catalyst layer can also be used on other types of membrane
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Hacquard, Alexandre. "Improving and Understanding Direct Methanol Fuel Cell (DMFC) Performance." Link to electronic thesis, 2005. http://www.wpi.edu/Pubs/ETD/Available/etd-050505-151501/.
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MATOS, BRUNO R. de. "Preparação e caracterização de eletrólitos compósitos NAFION-TiOsub(2) para aplicação em células a combustível de membrana de troca protônica." reponame:Repositório Institucional do IPEN, 2008. http://repositorio.ipen.br:8080/xmlui/handle/123456789/11615.
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Made available in DSpace on 2014-10-09T12:53:53Z (GMT). No. of bitstreams: 0Made available in DSpace on 2014-10-09T14:09:32Z (GMT). No. of bitstreams: 1 12641.pdf: 5742514 bytes, checksum: 8dbb5287cf99fe54ebb95b5b3406a880 (MD5)
Dissertação (Mestrado)
IPEN/D
Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP
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Muthukumarasamy, Ayyadurai Subasri. "Optical Sensing of Organic Contaminants through their Immobilization and Reaction Inside Perfluorosulfonic Acid Polymer Membranes." University of Cincinnati / OhioLINK, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1406821247.
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Alayyaf, Abdulmajeed A. "Synthesis of Two Monomers for Proton Exchange Membrane Fuel Cells (PEMFCs)." Digital Commons @ East Tennessee State University, 2016. https://dc.etsu.edu/etd/3015.
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The overall goal of this research is to synthesize two different monomers for proton exchange membrane (PEM) Fuel Cells. Such monomers are proposed to be polymerized to improve the efficiency and compatibility of electrodes and electrolytes in PEM fuel cells.
The first target is to synthesize 4-diazonium-3-fluoro PFSI zwitterionic monomer. Three steps were carried out in the lab. First one was the ammonolysis of 3-fluoro-4-nitrobenzenesulfonyl chloride. Second reaction was the bromination of Nafion monomer. The next coupling reaction, between brominated Nafion monomer and the 3-fluoro-4-nitrobenzenesulfonamide, was failed. The obstacles involve the harsh reaction condition and troublesome purification procedure.
The second target is to synthesize 5-nitro-1, 3-benzenedisulfonamide. According to the literature, this synthesis was also designed as three steps: 1)nitration of sodium 1, 3-benzenedisulfonate salt; 2)chlorination of sodium 5-nitro-1, 3-benzenedisulfonate salt; and 3)ammonolysis of 5- nitro-1, 3- benzenedisulfonyl chloride. This monomer is expected to be copolymerized for membrane electrolyte in PEM fuel cells.
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Zhou, Chun. "CHEMICAL DURABILITY STUDIES OF IONOMERS AND MODEL COMPOUNDS FOR FUEL CELL APPLICATIONS." Case Western Reserve University School of Graduate Studies / OhioLINK, 2008. http://rave.ohiolink.edu/etdc/view?acc_num=case1199478916.
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Osborn, Shawn James. "Morphological and Mechanical Properties of Dispersion-Cast and Extruded Nafion Membranes Subjected to Thermal and Chemical Treatments." Diss., Virginia Tech, 2009. http://hdl.handle.net/10919/37517.
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The focus of this research project was to investigate morphological and mechanical properties of both extruded and dispersion-cast Nafion® membranes. The project can be divided into three primary objectives; obtaining a fundamental understanding of the glass transition temperature of Nafion®, determining the effect of thermal annealing treatments on the morphology and mechanical properties of dispersion-cast Nafion®, and examination of dispersion-cast Nafion® subjected to an ex-situ, Fentonâ s chemical degradation test. Nafion®, a perfluorosulfonate ionomer, is considered a commercially successful semi-crystalline ionomer with primary applications in chlor-alkali cells and proton exchange membrane fuel cells.
With the aid of dynamic mechanical analysis (DMA) and dielectric spectroscopy (DS), we were able to provide definitive evidence for a genuine glass transition in Nafion®. DMA of Nafion® samples that were partially neutralized with tetrabutylammonium counterions showed a strong compositional dependence suggesting that the β-relaxations of H+-form Nafion® and the neutralized ionomers have the same molecular origin with respect to backbone segmental motions. Building upon our previous studies of the molecular and morphological origins of the dynamic mechanical relaxations of Nafion® neutralized with a series of organic ions, the glass transition temperature of H+-form Nafion® is now confirmed to be the weak β-relaxation centered at -20 °C. Dielectric spectra also showed this transition from the perspective of dipole relaxation. The signature of cooperative long range segmental motions in dielectric spectra was seen here, as with other polymers, mainly through the excellent agreement of the β-relaxation time-temperature dependence with the Vogel-Fulcher-Tammann equation.
We have also discovered that new dispersion-cast H+ form Nafion® membranes are susceptible to disintegration/dissolution when subjected to boiling methanol. In this work, we have achieved significant decreases in the percent solubility of H+-form Nafion® by either thermally annealing above 175 °C or solution-processing at 180 °C using a high boiling point solvent. Small Angle X ray Scattering (SAXS) displayed a change in the morphology of H+ form membranes with increasing annealing temperature by a shift in the crystalline scattering peak (q â 0.05 à 1) to lower q values. Counterion exchange of Nafion® from H+ to Na+ form had no influence on the membraneâ s susceptibility to disintegration in boiling methanol. In order to achieve mechanical stability in boiling methanol, Na+ form membranes had to be annealed at 275 °C for at least fifteen minutes. The SAXS data of annealed Na+ form membranes showed a dramatic decrease in crystalline order with annealing temperature, ultimately leading to the disappearance of the crystalline scattering peak after fifteen minutes at 275 °C. The onset of methanol stability with the melting of Nafion® crystallites suggests that chain entanglement is an important parameter in obtaining solvent stability.
With respect to chemical stability, we performed studies aimed at examining the effects of Fentonâ s Reagent on the resistance to radical attack of new generation, dispersion-cast Nafion®. Changes in the 19F solid-state NMR spectra of dispersion-cast Nafion® before and after chemical degradation via Fentonâ s Reagent predicts a rather random attack by â ¢OH and â ¢OOH radicals. Several membranes were also thermally annealed between 100-250 °C in an attempt to correlate crystallinity with chemical degradation kinetics of Nafion® via Fentonâ s Reagent. The results indicate that the effect of counterion exchange into the Na+ form was minimal, but the degree of thermal degradation had a tremendous effect on the fluoride release rate and chemical degradation kinetics. By exchanging the membranes into the Na+ form, thermal degradation was avoided, allowing us to study the role of crystallinity as a function of fluoride release. Ultimately, Nafion® crystallinity was deemed an important factor in deterring peroxide radical attack. As the percent crystallinity decreased with annealing temperature, the fluoride concentration in the resulting Fentonâ s media increased accordingly, indicating that the amorphous regions of the polymer are more susceptible to chemical degradation via peroxide radical attack.Ph. D.
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Aleksandrova, Elena [Verfasser], and E. [Akademischer Betreuer] Roduner. "Visualization of ionically active channels in the Nafion membrane by using electrochemical atomic force microscopy / Elena Aleksandrova. Betreuer: E. Roduner." Stuttgart : Universitätsbibliothek der Universität Stuttgart, 2013. http://d-nb.info/1029982171/34.
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Brunello, Giuseppe. "Computational modeling of materials in polymer electrolyte membrane fuel cells." Diss., Georgia Institute of Technology, 2013. http://hdl.handle.net/1853/48937.
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Fuel cells have the potential to change the energy paradigm by allowing more efficient use of energy. In particular, Polymer Electrolyte Membrane Fuel Cells (PEMFC) are interesting because they are low temperature devices. However, there are still numerous challenges limiting their widespread use including operating temperature, types of permissible fuels and optimal use of expensive catalysts. The first two problems are related mainly to the ionomer electrolyte, which largely determines the operating temperature and fuel type. While new ionomer membranes have been proposed to address some of these issues, there is still a lack of fundamental knowledge to guide ionomer design for PEMFC.
This work is a computational study of the effect of temperature and water content on sulfonated poly(ether ether ketone) and the effect of acidity on sulfonated polystyrene to better understand how ionomer material properties differ. In particular we found that increased water content preferentially solvates the sulfonate groups and improves water and hydronium transport. However, we found that increasing an ionomer’s acid strength causes similar effects to increasing the water content.
Finally, we used Density Functional Theory (DFT) to study platinum nano-clusters as used in PEMFCs. We developed a model using the atom’s coordination number to quickly compute the energy of a cluster and therefore predict which platinum atoms are most loosely held. Our model correctly predicted the energy of various clusters compared to DFT. Also, we studied the interaction between the various moieties of the electrolyte including the catalyst particle and developed a force field.
The coordination model can be used in a molecular dynamics simulation of the three phase region of a PEMFC to generate unbiased initial clusters. The force field developed can be used to describe the interaction between this generated cluster and the electrolyte.
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Chabé, Jérémy. "Étude des interactions moléculaires polymère-eau lors de l'hydratation de la membrane Nafion, électrolyte de référence de la pile à combustible." Grenoble 1, 2008. http://www.theses.fr/2008GRE10038.
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Le polymère Nafion est l'électrolyte de référence de la pile à combustible. Lorsqu'il est hydraté, il présente un conductivité élevée (10-2 S. Cm-1). Néanmoins cette conductivité chute à faible taux d'hydratation. L'ajout d'un compos hygroscopique dans la membrane, telle phosphate de zirconium (ZrP), a été proposé dans la littérature pour répondre à c problème. La conductivité est le fait de la structure du matériau, des mécanismes de diffusion du proton, et des interactions eaq polymère au sein de la membrane. Nous nous sommes intéressés à cette dernière partie du problème. Nous avons étudi' les mécanismes d'hydratation à l'échelle moléculaire pour les membranes Nafion puis Nafion-ZrP par technique d spectrométrie infrarouge sur toute la gamme d'hydratation. . Cette technique peut être couplée à une étude par dynamiqu moléculaire que nous avons initié sur le polymère Nafion. Nos résultats font état de 5 mécanismes d'hydratation successifs pour la membrane Nafion. L'ionisation des group sulfoniques S03H est très rapide en début d'hydratation. Elle est suivie d'un éloignement des protons H+ par rapport aux groupes sulfonates S03- et d'une réorganisation du réseau de liaisons H autour de ces groupes ioniques. Enfin une eau d type « bulk» apparaît vers 40% d'hydratation. Nous avons ainsi une « photographie» de la membrane à chaque tal d'hydratation. L'ajout d'un composé inorganique ZrP n'influe pas sur les mécanismes d'hydratation. D'après la comparaison entre nos mécanismes et la courbe de conductivité, il est nécessaire de dissocier tous les groupes sulfoniaues DOur atteindre une diffusion oDtimale du Droton, probablement assurée par le mécanisme de GrotthussThe Nafion is a polymer. Thanks to its high conductivity (up to ] 0-'< S. Cm-') at high relative humidity (RH), it is a reference electrolyt for a fuel cell. However its conductivity falls during low hydration conditions. To solve this problem, we can add a hygroscopic compound, like ziconium phosphate (ZrP), into the membrane. The conductivity is linked to the structure of the membrane, the proton diffusion mechanisms and the interactions between water molecules and the polymer; we are interested by this last field of research. Infrared spectroscopy are used to establish the hydration mechanisms at a molecular scale for a Nafion and a Nafion-ZrP membrane. This technique can be coupled with a molecular dynamic study, which we have begun for the Nafion. The inftared spectra ofNafion and Nafion-ZrP have been measured on the whole range of RH. We found 5 hydration mechanisms for the Nafion membrane. The ionisation of sulfonic groups S03H is very fast at the beginning ofhydration. Then the protons H+ move away from the sulfonate groups S03- and the net ofhydrogen bonds around these ionic groups changes. For a RH of 40%, bulk water appears inside the membrane. We have thus a "photograph" of the inner membrane at each stage of RH. The adding of an inoganic compound ZrP has no influence on the hydration mechanisms. According to the comparison between our mechanisms and the curve of conductivity, all the sulfonic groups have to be dissociated to reach optimal diffusion ofthe Droton, probablv assured bv the Grotthuss mechanism
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Nworie, Chimaroke. "Synthesis of a 4-(Trifluoromethyl)-2-Diazonium Perfluoroalkyl Benzenesuflonylimide (PFSI) Zwitterionic Monomer for Proton Exchange Membrane Fuel Cell." Digital Commons @ East Tennessee State University, 2014. https://dc.etsu.edu/etd/2346.
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In order to achieve a more stable and highly proton conducting membrane that is also cost effective, the perfluoroalkyl benzenesulfonylimides (PFSI) polymers are proposed as electrolyte for Proton Exchange Membrane Fuel Cells. 4-(trifluoromethyl)-2-diazonium perfluoro-3, 6-dioxa-4-methyl-7-octene benzenesulfonyl imide (I) is synthesized from Nafion monomer via a 5-step schematic reaction at optimal reaction conditions. This diazonium PFSI zwitterionic monomer can be further subjected to polymerization. The loss of the diazonium N2+ functional group in the monomer is believed to form the covalent bond between the PFSI polymer electrolyte and carbon electrodes support. All the intermediates and final products were characterized using 1H NMR, 19F NMR and IR spectrometry.
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Vierrath, Severin, Matthias Breitwieser, Matthias Klingele, Benjamin Britton, Steven Holdcroft, Roland Zengerle, and Simon Thiele. "The reasons for the high power density of fuel cells fabricated with directly deposited membranes." Elsevier, 2016. https://publish.fid-move.qucosa.de/id/qucosa%3A72520.
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In a previous study, we reported that polymer electrolyte fuel cells prepared by direct membrane deposition (DMD) produced power densities in excess of 4 W/cm2. In this study, the underlying origins that give rise to these high power densities are investigated and reported. The membranes of high power, DMD-fabricated fuel cells are relatively thin (12 μm) compared to typical benchmark, commercially available membranes. Electrochemical impedance spectroscopy, at high current densities (2.2 A/cm2) reveals that mass transport resistance was half that of reference, catalyst-coated-membranes (CCM). This is attributed to an improved oxygen supply in the cathode catalyst layer by way of a reduced propensity of flooding, and which is facilitated by an enhancement in the back diffusion of water from cathode to anode through the thin directly deposited membrane. DMD-fabricated membrane-electrode-assemblies possess 50% reduction in ionic resistance (15 mΩcm2) compared to conventional CCMs, with contributions of 9 mΩcm2 for the membrane resistance and 6 mΩcm2 for the contact resistance of the membrane and catalyst layer ionomer. The improved mass transport is responsible for 90% of the increase in power density of the DMD fuel cell, while the reduced ionic resistance accounts for a 10% of the improvement.
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ISIDORO, ROBERTA A. "Desempenho de membranas hibridas Nafion-TiO, e eletrocatalisadores de PtSn/C em celulas a combustivel do tipo PEM alimentadas com etanol e com Hsub(2)/CO em alta temperatura." reponame:Repositório Institucional do IPEN, 2010. http://repositorio.ipen.br:8080/xmlui/handle/123456789/9613.
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Made available in DSpace on 2014-10-09T12:28:39Z (GMT). No. of bitstreams: 0Made available in DSpace on 2014-10-09T13:57:29Z (GMT). No. of bitstreams: 0
Dissertacao (Mestrado)
IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP
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Colinart, Thibaut. "Gestion de l'eau et performances électriques d'une pile à combustible : des pores de la membrane à la cellule." Thesis, Vandoeuvre-les-Nancy, INPL, 2008. http://www.theses.fr/2008INPL039N/document.
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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 pileThis 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
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Fulati, Alimujiang, Ali Syed M. Usman, Muhammad H. Asif, Alvi Naveed Ul Hassan, Magnus Willander, Cecilia Brännmark, Peter Strålfors, Sara I. Börjesson, Fredrik Elinder, and Bengt Danielsson. "An intracellular glucose biosensor based on nanoflake ZnO." Linköpings universitet, Institutionen för teknik och naturvetenskap, 2010. http://urn.kb.se/resolve?urn=urn:nbn:se:liu:diva-57294.
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In this study, an improved potentiometric intracellular glucose biosensor was fabricated with immobilization of glucose oxidase on a ZnO nanoporous material. The ZnO nanoporous material with a wall thickness around 200 nm was grown on the tip of a borosilicate glass capillary and used as a selective intracellular glucose sensor for the measurement of glucose concentrations in human adipocytes and frog oocytes. The results showed a fast response within 4 s and a linear glucosedependent electrochemical response over a wide range of glucose concentration (500 nM-10 mM). The measurements of intracellular glucose concentrations with our biosensor were consistent with the values of intracellular glucose concentrations reported in the literature. The sensor also demonstrated its capability by detecting an increase in the intracellular glucose concentration induced by insulin. We found that the ZnO nanoporous material provides sensitivity as high as 1.8 times higher than that obtained using ZnO nanorods under the same conditions. Moreover, the fabrication method in our experiment is simple and the excellent performance of the developed nanosensor in sensitivity, stability, selectivity, reproducibility and anti-interference was achieved. All these advantageous features of this intracellular glucose biosensor based on functionalised ZnO nanoporous material compared to ZnO nanorods demonstrate a promising way of enhancing glucose biosensor performance to measure reliable intracellular glucose concentrations within single living cells.Original Publication:Alimujiang Fulati, Syed M. Usman Ali, Muhammad H. Asif, Naveed Ul Hassan Alvi, Magnus Willander, Cecilia Brännmark, Peter Strålfors, Sara I. Börjesson and Fredrik Elinder, An intracellular glucose biosensor based on nanoflake ZnO, 2010, Sensors and actuators. B, Chemical, (150), 2, 673-680.http://dx.doi.org/10.1016/j.snb.2010.08.021Copyright: Elsevier Science B.V., Amsterdam.http://www.elsevier.com/
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Uan-Zo-li, Julie Tammy. "The Effects of Structure, Humidity and Aging on the Mechanical Properties of Polymeric Ionomers for Fuel Cell Applications." Thesis, Virginia Tech, 2001. http://hdl.handle.net/10919/36259.
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The purpose of this work was to investigate the effects of structure, humidity and aging on the mechanical behavior of Nafion® and Dais® ionomers. It was determined that the majority of the properties of these membranes were controlled by the formation and growth of the ionic clusters that were the direct result of the ionic nature of these materials.
In the process of this study, the properties of Nafion® and sulfonated Dais® polymers were investigated by dynamic mechanical analysis and thermal gravimetric analysis and their water uptake and sorption and desorption isotherms were measured. A mastercurve and a shift factor plot were constructed for 60% sulfonated Dais® membrane.
It was determined that an increase in the degree of sulfonation raised the glass transition temperature of these materials by facilitating the formation of the ionic clusters which acted as physical crosslinks, thereby reducing the mobility of polymeric chains. Water was found to effectively plasticize the membranes, especially in the case of Dais® materials, by reducing the storage modulus and decreasing the structural integrity of the ionomers. The effect of pre-treatment of Nafion® was investigated and the glass transition temperature was found to increase as a function of the severity of the treatment procedure. The maximum water uptakes were determined for virgin and aged Nafion® and Dais® membranes and their vapor phase water sorption diffusion coefficients were calculated. The sorption process was found to follow pseudo-Fickian behavior, while the movement of water out of the membranes during the desorption process was determined to be controlled by mechanisms other than diffusion. Lastly, the effect of exposure of Nafion® and 30% sulfonated Dais® membranes to the saturated environment at elevated temperatures was investigated and found to result in the increase in the glass transition temperature of the materials. Results of the exposure effects on the diffusion properties of Nafion® and Dais® were inconclusive. Preliminary findings attributed the changes in the properties of the materials to the counteractive actions of physical aging and the growth of the ionic clusters.Master of Science
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Coudray, Mathias. "Procédé de recyclage des Assemblages Membrane Electrode (AME) de piles à combustible utilisant des liquides ioniques." Thesis, Lyon, 2019. https://n2t.net/ark:/47881/m6h70f5d.
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Le recyclage des assemblages membrane électrode (AMEs) des piles à combustible à membrane échangeuse de protons (PEMFC) est en enjeu important pour le développement du marché de ces piles fonctionnant à l’hydrogène. Dans ces AMEs se trouvent le platine (Pt), un métal précieux et rare qui conditionne majoritairement le coût total de la pile. Le recyclage du Pt est encore largement effectué par hydro ou pyrométallurgie ce qui entraîne le rejet de gaz toxiques et polluants dans l’environnement. Plusieurs études ont porté sur la mise en place d’une voie plus soutenable écologiquement que le traditionnel usage d’acides forts pour lixivier le platine. Le procédé proposé ici s’inscrit dans ce domaine de recherche en proposant une nouvelle voie de séparation des constituants de l’électrode de PEMFC en vu de leur recyclage par l’utilisation de liquides ioniques. Ceux-ci par leur stabilité thermique et chimique et leur non-volatilité peuvent permettre la mise en place d’un procédé de récupération du platine sûr. Après l’étude d’une sélection de liquides ioniques plusieurs d’entre eux, dont le P66614Cl (trihexyltetradécylphosphonium chlorure), ont permis la récupération du platine sous forme de nanoparticules détachées et stabilisées dans le liquide ionique. Une étude des interactions du liquide ionique avec chacun des composants de l’AME a permis de mieux comprendre les mécanismes d’extraction. Le liquide ionique interagit ainsi fortement avec l’ionomère présent dans la couche catalytique. Cette forte interaction ouvre la voie à un retraitement simultané du Nafion et du platine des AMEsRecovery of the protons-exchange membrane fuel cell (PEMFC) membrane electrode assemblies (MEAs) is an important issue for the growing of the fuel cells market. These MEAs contain platinum (Pt), which as a precious metal mainly influences the total cost of fuel cells. The recycling of Pt is still based to a great extent on hydro or pyrometallurgical techniques which produce toxic and pollutant gas emissions. Some studies aimed to set up processes to recycle platinum in a more sustainable way than traditional metal lixiviation using strong acids. The study here is part of this research field and is about a new way to separate the different components of the PEMFC electrode using ionic liquids for the recycling of these valuable materials. These liquids possess excellent thermal and chemical stability and their non-volatility can be useful to set up a safer way to recover platinum. A selection of ionic liquids was studied and some of them, including the P66614Cl (trihexyltetradecylphosphonium chloride), could be use to recover Pt nanoparticles detached from their carbon support and stabilized in the ionic liquid. A study on the interactions of ionic liquids and the components of the MEA allowed the extraction mecanisms to be better understood. Thus the ionics liquids interact strongly with Nafion in the catalyst layer which allows Pt nanoparticles to be recovered. These strong interactions set the stage for the simultaneous recycling of Nafion and Pt from MEAs
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Mrad, Christine. "Caractérisation ex-situ par RMN et IRM des transferts d'eau à l'interface membrane/électrode dans les piles à combustible PEMFC." Electronic Thesis or Diss., Université de Lorraine, 2023. http://www.theses.fr/2023LORR0358.
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Dans le cadre de la transition énergétique durable, les piles à combustible à membrane échangeuse de protons (PEMFC) sont considérées comme des alternatives prometteuses aux moteurs conventionnels. Elles offrent une conversion efficace de l'hydrogène en électricité sans émettre de polluant. Néanmoins, pour espérer un large déploiement de ces systèmes il est indispensable de réduire leur coût et améliorer leur durabilité. C'est pourquoi le projet européen « ALPE : Advanced Low-Platinum hierarchical Electrocatalysts for low-T fuel cells », dans lequel s'inscrit cette thèse, vise à réduire le coût des PEMFC en diminuant la quantité du catalyseur de platine (Pt) utilisée dans leurs électrodes, ciblant une réduction de 1.5 à 2 fois par rapport à l'état de l'art de 2019. Le fonctionnement des PEMFC repose essentiellement sur les réactions électrochimiques se produisant sur les sites catalytiques de Pt, et le transport protonique est étroitement lié à l'état d'hydratation de la membrane électrolyte (l'eau servant de vecteur pour les protons). Ce travail de thèse a donc pour objectif d'étudier l'impact de la réduction de la quantité de Pt sur les phénomènes de transport de l'eau à travers les interfaces membrane-électrode/air. Afin d'atteindre cet objectif, des dispositifs et des méthodologies expérimentaux permettant l'analyse de l'interface membrane/électrode par spectroscopie et imagerie de résonance magnétique (RMN/IRM) ont été développés. Dans un premier temps, l'étude se focalise sur l'étude d'une membrane seule de type Nafion® (N1110). Une analyse in-situ permettant de visualiser l'impact de l'histoire hygrothermale de la membrane sur les propriétés de l'eau est présentée. De plus, des expérimentations sous différentes conditions d'humidité relative, d'un côté et de l'autre de cette membrane, démontrent la capacité de notre approche à quantifier les résistances au transport de l'eau à interface de la membrane en les découplant des effets diffusifs. En complément, une modélisation 1D en régime permanent de la diffusion de l'eau à travers l'épaisseur de la membrane permet de déterminer l'évolution du coefficient de diffusion mutuelle de l'eau. Pour compléter notre analyse, une séquence de mesure en acquisition partielle a été conçue pour minimiser le temps d'acquisition des profils d'eau dans la membrane, ouvrant la voie à une étude en régime transitoire. Enfin, une comparaison des résistances d'interfaces entre une membrane seule et une membrane avec électrode(s) permet d'évaluer l'impact de l'ajout d'un dépôt d'une électrode et celui d'une variation de quantité de platine, sur les phénomènes de transport de l'eau. Les résultats mettent en lumière qu'en régime transitoire, il n'y a pas de différences significatives entre une membrane seule et un assemblage membrane/électrode (avec une seule ou deux électrodes). Toutefois, il apparaît que la présence de l'électrode et la quantité de platine semblent avoir un impact sur l'évolution des résistances d'interfaces en fonction de l'humidité relative de l'air alimentant la membraneIn the context of sustainable energy transition, Proton Exchange Membrane Fuel Cells (PEMFC) are considered promising alternatives to conventional engines. They offer efficient conversion of hydrogen into electricity without emitting pollutants. However, for the widespread deployment of these systems, it is essential to reduce their cost and improve their durability. This is the focus of the European project « ALPE: Advanced Low-Platinum hierarchical Electrocatalysts for low-T fuel cells », in which this thesis is situated. The project aims to reduce the cost of PEMFCs by decreasing the amount of platinum (Pt), catalyst used in their electrodes, targeting a reduction of 1.5 to 2 times compared to the state of the art in 2019. The operation of PEMFCs relies essentially on the electrochemical reactions occurring on the Pt catalytic sites, and proton transport is closely linked to the hydration state of the electrolyte membrane (water serving as a vector for protons). Therefore, the objective of this thesis is to study the impact of reducing the amount of Pt on the water transport phenomena across the membrane-electrode/air interfaces. In order to achieve this goal, experimental devices and methodologies for analyzing the membrane/electrode interface through spectroscopy and magnetic resonance imaging (NMR/MRI) have been developed. Initially, the study focuses on the examination of a single Nafion® membrane (N1110). An in-situ analysis that allows visualization of the impact of the membrane's hygrothermal history on the properties of water is presented. Furthermore, experiments under different relative humidity conditions on each side of the membrane demonstrate the capability of our approach to quantify interfacial resistances of water transfer while decoupling them from diffusive effects within the membrane. Additionally, a 1D steady-state model of the diffusion of water across the thickness of the membrane allows to determine the evolution of the mutual water diffusion coefficient. To complement our analysis, a partial acquisition measurement sequence has been designed to minimize the acquisition time of water profiles within the membrane, paving the way for a transient study. Finally, a comparison of interfacial resistances between a single membrane and a membrane with electrode(s) provides insights into the impact of adding an electrode deposit and varying the platinum loading on water transport phenomena. The results highlight that in transient conditions, there are no significant differences between a single Nafion® membrane and a membrane/electrode assembly (with one or two electrodes). However, it appears that the presence of the electrode and the amount of platinum seem to influence the evolution of interfacial resistances depending on the relative humidity (RH) of the air supplied to the sample
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Bacchi, Philippe. "Immobilisation de la glucose oxydase au sein de gels hydrophobes de nafion. Application au dosage du glucose par amperometrie." Université Joseph Fourier (Grenoble), 1996. http://www.theses.fr/1996GRE10246.
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Ce memoire porte sur l'utilisation de solutions concentrees de nafion (gels hydrophobes de nafion) pour l'immobilisation de la glucose oxydase (god) a la surface d'electrodes. Dans un premier temps, l'oxydase est contenue au sein d'une pate de carbone aqueuse, le gel du ionomere realisant un interface selectif entre systeme enzymatique immobilise et milieu de dosage. Cette separation des deux intervenants est imposee par leur incompatibilite, la confrontation de la god et de la solution hydrophobe du polymere conduisant a une perte des proprietes catalytiques de l'enzyme. L'etude du comportement de ce dispositif permet d'en degager les caracteristiques et de mettre en evidences ses principales limitations: mauvaise immobilisation du mediateur (espece electroactive chargee du transport d'electrons entre enzyme et electrode), inhibition de la reaction d'oxydation du glucose, miniaturisation poussee impossible. Ce travail est complete par une etude cinetique, realisee au moyen d'une electrode tournante, grace a laquelle la permeation du glucose au sein des gels peut etre quantifiee. La plupart des problemes de la precedente electrode etant imputables a son organisation en couches successives, nous cherchons dans un deuxieme temps a associer de facon plus intime god et solution hydrophobe du polymere. L'inclusion de l'enzyme dans des gels dont les solvants sont des alcools d'assez faible poids moleculaire, puis dans des gels prealablement hydrates, donne des gels ou le pouvoir catalytique de la god est conserve. Ces materiaux enzymatiques sont aisement deposes a la surface d'electrodes, realisant des dispositifs dont les dimensions peuvent etre reduites et dont la structure permet d'eviter l'inhibition de la glucose oxydase lors du dosage du glucose. Deux strategies d'immobilisation du mediateur dans ces capteurs amperometriques sont envisagees, la premiere est fondee sur l'affinite de quelques ferrocenes pour le solvant hydrophobe constitutif du gel, la seconde sur l'affinite de l'oxygene pour les chaines perfluorees du nafion
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Iezzi, Renato Caio. "Tolerância ao CO da reação de oxidação de hidrogênio por mecanismos de oxidação: efeitos do substrato do eletrocatalisador." Universidade de São Paulo, 2016. http://www.teses.usp.br/teses/disponiveis/75/75134/tde-13122016-092607/.
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O alto custo da produção de hidrogênio puro para ser usado como combustível para uma reação de oxidação de hidrogênio (ROH) em células a combustível faz com que seja atrativo o uso de hidrogênio gerado através da reforma de combustíveis fóssil. Entretanto, o hidrogênio gerado por reforma de outros combustíveis possui contaminantes como CO, que por se adsorver fortemente sobre a superfície do eletrodo de platina, prejudica em muito o processo de oxidação do hidrogênio. Assim o estudo de novos catalisadores mais resistentes a essa contaminação e de outros mecanismos que contribuam para um melhor desempenha de uma célula a combustível do tipo PEMFC, se faz necessário. Esse presente trabalho tem como objetivo o estudo dos catalisadores PtMo/C - 80:20, PtMoO2/C, PtMoO3/C, que foram sintetizados, e PtMoPtRu/C, PtMoPt3Fe/C e PtMoPt3FePtRu/C que foram obtidos através da mistura do PtMo/C - 80:20 sintetizado com os PtRu/C e PtFe/C que são comerciais, através da realização de curvas de polarização no estado estacionário, voltametrias cíclicas e degradação eletroquímica acelerada. Também foi avaliada a eficiência da membrana de Aquivion®, com relação ao cruzamento de subprodutos da degradação dos eletrodos, através de curvas de polarização no estado estacionário, voltametrias cíclicas e variação de temperatura de operação da célula PEMFC. O método usado para a síntese dos eletrocatalisadores se mostrou eficiente na obtenção dos catalisadores, obtendo-se os catalisadores com proporção bem próxima da desejada. Os resultados mostraram uma grande estabilidade química dos catalisadores mistos sendo o PtMoPt3FePtRu/C o mais estável e o PtMoPtRu/C o catalisador mais ativo para uma ROH. Os experimentos com a membrana de Aquivion® mostraram que essa é capaz de diminuir o cruzamento de subprodutos da degradação dos eletrodos.The high cost of pure hydrogen production to be used as fuel for a hydrogen oxidation reaction (HOR) in fuel cells makes it attractive to use hydrogen generated by reforming of fossil fuels. However, the hydrogen generated by reforming other fuels has contaminants such as CO, which adsorb strongly on the surface of the platinum electrode, affect much the hydrogen oxidation process. Thus the study of new catalysts more resistant to such contamination and other mechanisms that contribute to a better performs of a fuel cell of the PEMFC type, it is necessary. This present study aims to study of catalysts PtMo/C - 80:20 PtMoO2/C, PtMoO3/C, which were synthesized and PtMoPtRu/C, PtMoPt3Fe/C and PtMoPt3FePtRu/C which were obtained by mixing the PtMo/C - 80:20 synthesized with PtRu/C and PtFe/C which are commercial, by performing polarization curves at steady state, cyclic voltammetry and electrochemical degradation accelerated. It also evaluated the efficiency of Aquivion® membrane with respect to the cross-products of degradation of the electrodes by means of polarization curves at steady state, cyclic voltammetry and operating temperature range of the cell PEMFC. The method used for the synthesis of electrocatalysts proved efficient in obtaining the catalysts, the catalysts obtaining very near to the desired proportion. The results showed a great chemical stability of the mixed catalyst being PtMoPt3FePtRu/C more stable and PtMoPtRu/C as catalyst more active for HOR. Experiments with Aquivion® membrane have shown that this can reduce the cross-products of degradation of the electrodes.
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Alharbi, Helal. "Synthesis of Diazonium N-(Perfluoroalkyl) Benzenesulfonimide Polymers for Proton Exchange Membrane Fuel Cells (PEMFCs)." Digital Commons @ East Tennessee State University, 2019. https://dc.etsu.edu/etd/3601.
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The objective of the research is to synthesize the diazonium N-(perfluoroalkyl) benzenesulfonimide (PFSI)zwitterionicpolymers as electrolytes in polymerelectrolyte membrane (PEM) fuel cells. The proposed diazoniumPFSI zwitterionic polymer (I) is expected to enhance the thermal and chemical stability, increase the proton conductivity of electrolytes, and improve the catalyst efficiency for PEM fuel cells. Synthesis of the perfluorobenzoyl peroxide initiator, homopolymerization of perfluoro (3-oxapent-4-ene) sulfonyl fluoride,coupling reaction with4-sulfamonylacetanilide, couplingreaction with 4-nitrobenzene sulfonyl amide, n-deacetylation reaction, and diazotization reactionhave been carried outsuccessfully in the lab. The intermediate chemicals are characterized by GC-MS, IR, NMR, and GPC spectroscopies.
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DRESCH, MAURO A. "Sintese e caracaterizacao eletroquimica de membranas hibridas nafion-SiOsub(2) para aplicacao como eletrolito polimerico em celulas a combustivel tipo PEM." reponame:Repositório Institucional do IPEN, 2009. http://repositorio.ipen.br:8080/xmlui/handle/123456789/9477.
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Made available in DSpace on 2014-10-09T12:27:09Z (GMT). No. of bitstreams: 0Made available in DSpace on 2014-10-09T13:56:18Z (GMT). No. of bitstreams: 0
Dissertacao (Mestrado)
IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP
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De, Moor Gilles. "Approche multi-échelle des mécanismes de vieillissement des coeurs de pile à combustible." Thesis, Université Grenoble Alpes (ComUE), 2015. http://www.theses.fr/2015GREAI049/document.
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Malgré d'importants progrès ces dix dernières années, les piles à combustible de type PEMFC (à membrane échangeuse de protons) souffrent toujours de fin de vie prématurée. Le catalyseur et la membrane, principaux constituants du cœur de la pile, sont les deux éléments principalement mis en cause. Ce travail a pour objectif de comprendre les modes de rupture et de dégradation de la membrane électrolyte durant le fonctionnement. Différents types de vieillissement ont été analysés, à la fois en laboratoire mais également sur des systèmes ayant fonctionné sur site en conditions réelles d'opération (jusqu'à 13000 heures). Au travers une approche multi-échelle (du système macroscopique à l'analyse des propriétés macromoléculaires de la membrane) et d'une utilisation systématique (plusieurs centaines d'échantillons analysés), des scénarios de dégradation ont été établis. Dans un premier temps, des outils de caractérisation macroscopiques ont été spécifiquement développés pour sonder rapidement l'ensemble des cellules d'un stack. Ces outils permettent d'identifier les défauts inter et intra-cellule tout en discriminant les propriétés barrières aux gaz des propriétés d'isolation électronique des membranes, tous deux responsables des courants de fuite en système. Cette approche systématique sur l'ensemble des échantillons a mis en évidence des zones spécifiques favorisant la dégradation prématurée des membranes. Dans un second temps, des caractérisations physico-chimiques ciblées dans ces zones de défaillance ont révélé une dégradation fortement localisée et principalement favorisée par des conditions opératoires spécifiques dans les zones d'entrée des gazIn spite of strong improvements in fuel cell design this last ten years, Proton Exchange Membrane Fuel Cell are still suffering of premature end of life. Failure of the heart of fuel cell, composed of membrane and catalysts, is commonly responsible for fuel cell shutdown. This work brings an original contribution in understanding membrane degradation mechanisms. Different ageing tests were analyzed, in laboratory as well as in real life operating conditions (up to 13000 hours of solicitations). Within a multi-scale approach, from macroscopic to microscopic, and with a systematic usage (hundreds of samples fully characterized), some degradation mechanisms were established. Firstly, macroscopic tools were specifically developed to rapidly track state of health of all the cells from each stack. With the help of these tools, we were able to identify defects inter and intra-cell. It was also possible to discriminate between gas crossover or electronic short-circuit defects, both responsible for current leaks. This systematic approach on each samples put forward some specific areas within the membrane where degradation was promoted. Secondly, physico-chemical characterizations were performed on membrane targeted areas. It was shown that membrane degradation is strongly localized in some specific channels of the bipolar plates and favored by specific operating conditions in the gaz inlets areas
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Wiles, Kenton Broyhill. "High Performance Disulfonated Poly(arylene Sulfone) Co- and Terpolymers For Proton Exchange Membranes For Fuel Cell And Transducer Applications: Synthesis, Characterization And Fabrication Of Ion Conducting Membranes." Diss., Virginia Tech, 2005. http://hdl.handle.net/10919/27096.
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The results described in this dissertation have demonstrated several alternative proton exchange membranes (PEM) for hydrogen-air and direct methanol fuel cells (DMFC) that perform as well or better than the state of the art Nafion perfluorosulfonic acid membrane. Direct aromatic nucleophilic substitution polycondensations of disodium 3,3â S-disulfonate-4,4â S-difluorodiphenylsulfone (SDFDPS), 4,4â S-difluorodiphenylsulfone (DFDPS) (or their chlorinated analogs, SDCDPS, DCDPS) and 4,4â S-thiobisbenzenethiol (TBBT) in the presence of potassium carbonate were investigated. Electrophilic aromatic substitution was employed to synthesize the SDFDPS or SDCDPS comonomers in high yields and purity. High molecular weight disulfonated poly(arylene thioether sulfone) (PATS) copolymers were easily obtained using the SDFDPS monomers, but in general, slower rates and a lower molecular weight copolymer was obtained using the analogous chlorinated monomers. Tough and ductile membranes were solution cast from N,N-dimethylacetamide for both series of copolymers. The degrees of disulfonation (20-50%, PATS 20-50) were controlled by varying the ratio of disulfonated to unsulfonated comonomers. Composite membranes were prepared by homogeneous solution blending the copolymers with phosphotungstic acid (PTA) in dimethylacetamide (DMAc). The composite PATS membranes exhibited moderate PTA molecule water extraction after acidification treatments performed at either room or boiling temperatures. The membranes containing HPA showed improved conductivity at high temperatures (120 ¢XC) and low relative humidities when compared to the pure copolymers.
Molecular weight of the copolymers plays a critical role in the overall copolymer physical behavior. It is well known that molecular weight has an enormous impact on practically all of the physical properties of polymeric systems. This dissertation discusses the influence of molecular weight on the characteristics of a specific family of PEM PATS copolymers. This study elucidated that the lower molecular weight materials did indeed behave differently than the higher molecular weight copolymers. Specifically, the water uptake and permeability to methanol decreased with increasing molecular weight. Furthermore, the fully hydrated mechanical properties also improved with molecular weight.
The synthesis and fabrication of 45 mole percent disulfonated poly(arylene ether phenyl phosphine oxide diphenyl sulfone) terpolymer-heteropolyacid (HPA) composite membranes and membrane electrode assemblies were chosen for detailed investigation. A series of 45 mole percent disulfonated biphenol-based poly(arylene ether phenyl phosphine oxide diphenyl sulfone) terpolymers (BPSH45-PPO) were also synthesized by nucleophilic aromatic substitution polymerizations. The level of disulfonation was constant at 45 mole percent providing a compromise between high conductivity at low humidity and reasonable mechanical properties in liquid water. The amounts of 4,4¡¦-difluorodiphenyl phenyl phosphine oxide comonomer incorporated into the terpolymer backbone were precisely controlled from 0-50 mole percent relative to the 4,4¡¦-dihalodiphenyl sulfone. Phosphine oxide moieties were employed to enhance the interactions with the PTA relative to the pure copolymer. The composite BPSH45-PPO membranes exhibited lower HPA molecule water extraction after acidification at room and boiling temperatures, which was ascribed to the strong hydrogen and polar interactions between the phosphine oxide moiety and functional groups on the HPA. The membranes containing HPA displayed improved conductivity at high temperatures and low relative humidities when compared to the pure terpolymer samples. The increase of proton conductivity was attributed to the water retention characteristics of the HPA molecules, which allowed enhanced mobility of the protons even at lower humidification levels, providing superior hydrogen-air fuel cell performance.
The effect of hexafluoroisopropylidene bisphenol (6FBP) incorporation into 45 mole percent disulfonated poly(arylene ether sulfone) copolymers was investigated. This novel series of directly disulfonated poly(arylene ether sulfone) copolymers with various mole ratios of the 6FBP were synthesized in high molecular weight. The levels of fluorination within the statistically random copolymer architecture were varied from 0-100 mole percent using 6FBP and the correct stoichiometric amount of 4,4¡¦-biphenol. The 6FBP monomer was introduced to decrease the water swelling and improve bonding characteristics with Nafion-bonded electrodes. Indeed, water uptake decreased with increasing incorporation of the 6FBP monomer into the terpolymer. This suggested that the hydrophobic fluorinated material aided in water repulsion of the system. Proton conductivity decreased slightly as the amount of fluorination increased, which was interpreted to be due to the decrease in the ion-exchange capacity. High temperature hydrogen/air fuel cell experiments indicated better Nafion-bonded electrode adhesion for the partially fluorinated materials, as depicted by high temperature (120 ¢XC) and low humidity (50% RH) hydrogen-air fuel cell performance.
Investigations into polymeric electromechanical transducers were based on poly(arylene sulfone) ion-exchange membranes bonded between two conductive metal layer electrodes. Imposed deformations and small electric fields allowed similar explorations of both sensing and actuation applications. These copolymers produced larger sensitivities than the benchmark Nafion systems, which was interpreted as being due to their higher hydrated moduli. Methodologies for better defining the morphology of the electrodes were identified to enhance the capacitance and effective interfacial area of the conductive electrodes. The new procedures afforded major improvements to performance and transduction. Transducer actuation at lower frequencies was improved by employing a new direct assembly electrode fabrication technique that suggested a strong correlation between the capacitance and charge motion.Ph. D.
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Rossi, Marco, Thomas Wallmersperger, Jorge Alejandro Ramirez, and Paola Nardinocchi. "jz Thermodynamically consistent electro-chemo-mechanical model for polymer membranes." SPIE, 2018. https://tud.qucosa.de/id/qucosa%3A35160.
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Nafion membranes, are polymeric thin films widely employed in micro-batteries and fuel cells. These devices are expected to play a key role in the next generation energy systems for use in vehicles as a replacement to combustion engines. In fact, a minimum environmental impact is guaranteed by reduced carbon dioxide emissions. It is usually complicated to investigate the behavior of thin membranes through experiments. Therefore, numerical simulations are carried out in order to enable a better understanding of the phenomena and of the multi-field couplings occurring in polymeric membranes.
A continuum-based, three-dimensional and electro-chemo-mechanical (ECM) model for a hydrated polymer membrane is presented. Different effects are taken into account: (i) mechanics, (ii) water uptake, (iii) ion transport, and (iv) electrostatics. The dissipation inequality drives the choice of the suitable constitutive equations of the multi-physics theory. In the mechanical field, an additive decomposition of the deformation gradient in (i) a distortion part, related to the ion motion, and (ii) an elastic part, is assumed. The multi-field model is numerically solved within the finite element framework. Time-dependent simulations are performed by using the commercial tool COMSOL Multiphysics. Furthermore, two closed form solutions are obtained by using (i) a one-dimensional reduced model and (ii) an approach based on the bar theory with an electro-chemical distortion field.
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Ressam, Ibitissam. "Élaboration et caractérisation de nouvelles membranes composites à conduction protonique pour les piles à combustible." Thesis, Paris 6, 2017. http://www.theses.fr/2017PA066732.
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Le Nafion a été considéré comme électrolyte modèle pour les piles à combustible (PAC), grâce à sa stabilité thermique et chimique ainsi que sa bonne conductivité protonique. Cependant, la conductivité protonique du Nafion se détériore à des taux d’humidité < 50% et à des températures >80°C. Pour cette raison de nouvelles membranes hybrides ont été élaborées afin d’en améliorer les performances. Plusieurs pistes ont été envisagées comme par exemple i) Membranes à base de chitosane, considéré comme le second polysaccharide le plus abondant après la cellulose. Ce polymère naturel permet d’assurer la stabilité physique et chimique de la membrane en présence d’eau, sans oublier son coût de revient qui reste moins cher en comparaison avec celui du Nafion et ii) Membranes à base de Nafion et d'argiles fibreuses (HNT), ces dernières confèrent à la membrane une conductivité protonique élevée en construisant des voies de transfert larges et continues. Cela permet aussi d'améliorer les propriétés thermiques et mécaniques des PEM. Notre étude est basée sur l'élaboration de membranes composites, nafion, chitosane et HNT. Des mesures de conductivité ont été entreprises et les valeurs obtenues comparées à celles du nafion. Des mesures d'ac-électrogravimétrie ont aussi été entreprises afin de mieux aborder les mécanismes de conductionThe perfluoro-sulfonated ionomer membranes are employed as separators in many industrialapplications such as fuel cells, chloro-alkali industry, electrodialysis and gaining inclininginterest in aqueous rechargeable or redox-flow batteries where the knowledge of their ionictransport and transfer properties is fundamental.Particularly, Nafion is adopted as a referencemembrane for polymer electrolyte membrane (PEM) fuel cells due to its thermal stability andgood proton conductivity. However, Nafion membranes have several disadvantages such as a decrease in the proton conductivity at low relative humidity (<50%) and high temperatures(>80°C), and excessive dimensional changes due to the swelling/deswelling, leading tomechanical instabilities.To circumvent these problems, novel proton conducting membraneshave been developed, either by completely replacing or by using organic and/or inorganiccomponents to Nafion.3 In this regard, a large spectrum of membranes have been elaboratedconsidering many attributes such as high proton conductivity, physical separation between theanode and the cathode and fuel barrier characteristics, good chemical and physical stability andlow elaboration cost of the membrane. Two types of additives were examined to improve the performances, particularly : Membranes based on Nafion with Chitosan biopolymer. This naturel polymer is consideredas the second most abundant polysaccharide after cellulose.6 Chitosan improves the physical andchemical stability of the membrane in the presence of water, and it is considered as a less costlyadditive to Nafion7.The improvement of the proton conductivity with pristine chitosan isessentially challenging. Previous studies demonstrated that vehicularandGrotthuss mechanismjointly govern the proton transfer in chitosan membranes.In the vehicular mechanism, the protons diffuse together with solvent molecules in the form of hydronium ions byforming acomplex such as H5O2+ and H9O4+. In the Grotthuss mechanism, however, the protons jump fromone solvent molecule or functional group to the next by the continuous formation and breakingof hydrogen bonds. Membranes based on Nafion with Halloysite nanotubes (HNT). These clays confer to themembrane high proton conductivity by constructing large and continuous conductionpathways.These inorganic additives also improve the thermal and mechanical properties of PEM. Composite membranes of Nafion/Chitosan- SO3H and Nafion/HNT-SO3H are prepared. Theresulting composite membranes were studied by various conventional structural characterizationtechniques. H+ conductivity measurements were performed and the values obtained are higherthan those of pristine Nafion at various relative humidity (RH%) levels and temperatures (30°C-80°C). Our results highlight the beneficial character of functionalized chitosan biopolymer andHalloysite nanotube clays as additives to improve PEM performances
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von, Kraemer Sophie. "Membrane Electrode Assemblies Based on Hydrocarbon Ionomers and New Catalyst Supports for PEM Fuel Cells." Doctoral thesis, KTH, Tillämpad elektrokemi, 2008. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-9208.
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The proton exchange membrane fuel cell (PEMFC) is a potential electrochemicalpower device for vehicles, auxiliary power units and small-scale power plants. In themembrane electrode assembly (MEA), which is the core of the PEMFC single cell,oxygen in air and hydrogen electrochemically react on separate sides of a membraneand electrical energy is generated. The main challenges of the technology are associatedwith cost and lifetime. To meet these demands, firstly, the component expensesought to be reduced. Secondly, enabling system operation at elevated temperatures,i.e. up to 120 °C, would decrease the complexity of the system and subsequentlyresult in decreased system cost. These aspects and the demand for sufficientlifetime are the strong motives for development of new materials in the field.In this thesis, MEAs based on alternative materials are investigatedwith focus on hydrocarbon proton-conducting polymers, i.e. ionomers, and newcatalyst supports. The materials are evaluated by electrochemical methods, such ascyclic voltammetry, polarisation and impedance measurements; morphological studiesare also undertaken. The choice of ionomers, used in the porous electrodes andmembrane, is crucial in the development of high-performing stable MEAs for dynamicoperating conditions. The MEAs are optimised in terms of electrode compositionand preparation, as these parameters influence the electrode structure andthus the MEA performance. The successfully developed MEAs, based on the hydrocarbonionomer sulfonated polysulfone (sPSU), show promising fuel cell performancein a wide temperature range. Yet, these membranes induce mass-transportlimitations in the electrodes, resulting in deteriorated MEA performance. Further,the structure of the hydrated membranes is examined by nuclear magnetic resonancecryoporometry, revealing a relation between water domain size distributionand mechanical stability of the sPSU membranes. The sPSU electrodes possessproperties similar to those of the Nafion electrode, resulting in high fuel cell performancewhen combined with a high-performing membrane. Also, new catalystsupports are investigated; composite electrodes, in which deposition of platinum(Pt) onto titanium dioxide reduces the direct contact between Pt and carbon, showpromising performance and ex-situ stability. Use of graphitised carbon as catalystsupport improves the electrode stability as revealed by a fuel cell degradation study.The thesis reveals the importance of a precise MEA developmentstrategy, involving a broad methodology for investigating new materials both as integratedMEAs and as separate components. As the MEA components and processesinteract, a holistic approach is required to enable successful design of newMEAs and ultimately development of high-performing low-cost PEMFC systems.QC 20100922
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Martinez, Mathieu. "Nouvelles membranes conductrices protoniques à l’état anhydre." Grenoble INPG, 2009. http://www.theses.fr/2009INPG0173.
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Au cours de cette étude, nous nous sommes intéressés à l’influence de l’acide (sa force, sa structure, sa taille, sa nature, etc. ) et de l’ajout d’eau sur les caractéristiques des CLIPs. Nous avons pu démontrer que la stabilité thermique dépend fortement de la basicité et de la nature de l’anion (Td > 300°C). Les conductivités sont plutôt influencées par la structure et la taille de l’anion, les meilleures conductivités étant obtenues pour des anions de super acide de petite taille. Pour ce qui est des membranes, celles à base de Nafion® ont démontré une très bonne conduction protonique mais une tenue mécanique insuffisante. Les membranes denses à base de polysulfone ont des propriétés très insuffisantes tant du point de vue mécanique que de la conduction. Les dernières membranes étudiées à base de polymères macropreux de type polyimide ont montré les meilleures performances dans tous les domaines étudiés et semblent les mieux adaptées pour l’application PEMFC « Haute température »The purpose of this thesis was to study the effect of the starting acid (strength, structure, size, type…) and of the water concentration on the CLIP’s properties. We showed that thermal stability was controlled by the anion’s basicity and its nature (Td > 300°C). On the other hand, conductivity has been found dependent on the size and the type of the anion (best conductivities for small sized super acid anion). Membranes are based on the association of a CLIP with a polymer (Nafion®, sulfonate polysulfone, polyimide). Nafion® based membranes showed good conductivities but poor mechanical properties at high temperature. Sulfonated polysulfone based membranes have both low toughness and low conductivities. The last studied electrolyte, based on macroporous polyimide, exhibited the highest conductivities and the best thermomechanical properties; they seem to be the most adapted membranes for the PEMFC application
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Escribano, Sylvie. "Optimisation de nouvelles électrodes pour piles à combustible hydrogène/oxygène à membrane électrolyte polymère." Grenoble INPG, 1995. http://www.theses.fr/1995INPG0148.
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Ce travail concerne l'optimisation de nouvelles electrodes pour piles a combustible hydrogene/oxygene a membrane electrolyte polymere. L'energie electrique est fournie par la recombinaison en eau de l'hydrogene et de l'oxygene, respectivement oxyde et reduit sur deux electrodes separees par la membrane electrolyte, ici du nafion. L'objectif est de realiser des electrodes a tres faibles chargements en platine (utilise comme catalyseur) mais fournissant de bonnes performances electrochimiques. Une etude theorique succincte donne des informations sur le comportement des piles en fonction de certaines caracteristiques des assemblages electrodes/membrane (aem). La zone active des electrodes (contenant le platine) est deposee par pulverisation soit sur des tissus de carbone contenant un agent hydrophobe (zone diffusionnelle) soit sur la membrane electrolyte. Les aem sont formes par pressage a chaud des trois elements zone diffusionnelle-zone active-membrane. L'interet et l'influence de plusieurs parametres d'elaboration sont analyses hors fonctionnement par des techniques de caracterisation morphologique, comme la microscopie electronique et la thermoporometrie, mais aussi par voltamperometrie cyclique. Les tests en pile sont enfin utilises pour l'evaluation des performances electrochimiques, representees par les courbes de polarisation