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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
231

Electrolytes polymère nano-structurés à base de liquides ioniques pour les piles à combustible hautes températures / Nano-structured polymer electrolytes based on ionic liquids for high temperature-pemfc

Sood, Rakhi 06 December 2012 (has links)
Les membranes à base de liquides ioniques à conduction protonique (PCIL) sont très prometteuses comme électrolytes des piles à combustible haute température (HT- PEMFC) du fait de leur forte conductivité et stabilité à des températures supérieures à 100°C. L'objectif de cette thèse est de réaliser une étude approfondie sur l'évolution de la morphologie et des propriétés fonctionnelles, des membranes à base de liquides ioniques, avec i) la concentration en PCIL, ii) la méthode d’élaboration et iii) la structure chimique du PCIL. Afin de prouver la potentialité de ces membranes dans le HT-PEMFC, des tests préliminaires en pile sont réalisés et les phénomènes de dégradation des PCIL et des membranes en présence de peroxyde d'hydrogène sont étudiés. La première partie de ce travail est focalisée sur la caractérisation des membranes de Nafion® neutralisées avec le triéthylamine (Nafion-TEA) et gonflées avec triflate de triéthylammonium (TFTEA). Il a été montré que dans le Nafion-TEA sec, les cations présentent une organisation de type « string like » à l'interface hydrophobe-hydrophile. L’introduction du TFTEA dans la membrane Nafion-TEA ne détruit pas sa nano-structuration, mais augmente de manière significative la conductivité ionique du système. La deuxième partie de ce travail nous a permis d'établir que les membranes dopées élaborées par coulée-évaporation présentent une meilleure organisation et une meilleure tenue thermomécanique par rapport à celles obtenues par gonflement. La troisième partie de ce travail est focalisée sur l’étude de l'impact de la nature chimique du PCIL sur la morphologie et les propriétés fonctionnelles des membranes de Nafion-TEA. Il a été démontré que les PCILs avec longues chaînes perfluorées ne modifient pas la nano-structuration du Nafion-TEA. Ceci a un impact fort sur les propriétés de conductivité, de sorption d’eau et sur les propriétés thermomécaniques de la membrane. Dans la dernière partie, des Ionomères aromatiques ont été synthétisés afin de remplacer le Nafion-TEA. Malgré la structure similaire de la chaîne latérale des Ionomères aromatiques et du Nafion®, les membranes à base d’Ionomères aromatiques et TFTEA ne présentent aucune nano-structuration. De plus l’effet plastifiant du TFTEA est plus notable dans le cas des Ionomères aromatiques probablement du fait d’une distribution aléatoire des fonctions ioniques dans la membrane polymère. / The polymer electrolyte membranes based on Proton Conducting Ionic liquids (PCIL) are very promising systems for the high temperature-PEMFC technology owing to their good ionic conductivity and stability at temperatures above 100oC. The objective of this thesis work is to achieve a profound study on the evolution of morphology and consequent functional properties of the PCIL based polymer electrolyte membranes in function of: i). concentration of the PCIL, ii). the method of elaboration and iii). chemical structure of the PCIL. To demonstrate the potential of these membranes in HT-PEMFC, preliminary tests have been carried out in the fuel cell stack and degradation phenomena associated with PCILs and membranes in the presence of hydrogen peroxide have been studied. The first part of this work is focused on the characterization of Nafion® membranes neutralized with triethylamine (Nafion-TEA) and swollen with triethylammonium Triflate (TFTEA). It has been shown that Nafion-TEA exhibits a single layer string-like organization of inter-digited Triethylammonium cations at the hydrophobic-hydrophilic interface when in anhydrous state. The introduction of TFTEA into Nafion-TEA membrane does not destroy its nano-structuration but significantly boosts the anhydrous ionic conductivity and hydrophilicity of the system. The second part of this work has permitted us to establish the fact that doped membranes prepared by casting method have better organization and better thermo-mechanical properties compared to those obtained by swelling method. Third part of this work focuses on the impact of the chemical nature of the PCIL on the morphology and functional properties of Nafion-TEA membranes. It has been demonstrated that the PCILs with long perfluorinated chain length do not modify the nano-structuration of Nafion-TEA membranes at all. This has a strong impact on the ion-conducting, water-sorption and thermo-mechanical properties of the membrane. In the last part, aromatic ionomers were synthesized in order to replace Nafion-TEA in such PCIL based system. Despite the similar structure of the side chain of the synthesized aromatic ionomers and Nafion®, the membranes based on aromatic ionomers and TFTEA do not present any nano-structuration. Moreover, the plasticizing effect of TFTEA is more noticeable in the case of aromatic ionomers probably due to a random distribution functions in the ionic polymer membrane.
232

Poly (2,5-benzimidazole) based polymer electrolyte membranes for high temperature fuel cell applications

Liu, Qingting January 2010 (has links)
Polymer electrolyte membrane fuel cells (PEMFCs) are one of the most promising clean technologies under development. However, the main obstacles for commercialising PEMFCs are largely attributed to the technical limitations and cost of current PEM materials such as Nafion. Novel poly(2,5-benzimidazole) (ABPBI)/POSS based polymer composite electrolyte membranes with excellent mechanical and conductivity properties were developed in this project including (I) ABPBI, polybenzimidazole (PBI) and their copolymers were synthesised by solution polymerisation and their chemical structures were confirmed by FTIR and elemental analysis. ABPBI/ActaAmmonium POSS (ABPBI/AM) and ABPBI/TriSilanolPhenyl POSS (ABPBI/SO) composites were also synthesised in situ. High quality polymer and composite membranes were fabricated by a direct cast method; and (II) The mechanical and thermal properties, microstructure and morphology, water and H3PO4 absorbility and proton conductivity of phosphoric acid doped and undoped ABPBI and ABPBI/POSS composite membranes were investigated. SEM/TEM micrographs showed that a uniform dispersion of POSS nano particles in ABPBI polymer matrix was achieved. The best performances on both mechanical properties and proton conductivities were obtained from the ABPBI/AM composite membrane with 3 wt% of POSS (ABPBI/3AM). It was found that both the water and H3PO4 uptakes were increased significantly with the addition of POSS due to formation of hydrogen bonds between the POSS and H2O/H3PO4, which played a critical role in the improvement of the conductivity of the composite membranes at temperatures over 100oC. ABPBI/3AM membranes with H3PO4 uptake above 117% showed best proton conductivities at both hydrous and anhydrous conditions from room temperature to 160oC, which is comparable with the conductivity of commercial Nafion 117 at 20oC in water-saturated condition, indicating that these composite membranes could be excellent candidates as a polymer electrolyte membrane for high temperature applications. A new mechanism for illustrating the improved proton conductivity of composite membranes was also developed.
233

Materials Reliability in PEM Fuel Cells

Mølmen, Live January 2021 (has links)
As part of the global work towards reducing CO2 emissions, all vehicles needs to be electrified, or fueled by green fuels. Batteries have already revolutionised the car market, but fuel cells are believed to be a key energy conversion system to be able to electrify also heavy duty vehicles. The type of fuel cell commercially available for vehicles today is the polymer electrolyte membrane fuel cell (PEMFC), but for it to be able to take a larger market share, the cost must be reduced while sufficient lifetime is ensured. The PEMFC is a system containing several components, made of different materials including the polymer membrane, noble metal catalyst particles, and metallic bipolar plate. The combination of different materials exposed to elevated temperature, high humidity and low pH make the PEMFC components susceptible to corrosion and degradation. The noble metal catalyst is one of the major contributors to the high cost. In this work, the latest research on new catalyst materials for PEMFCs are overviewed. Furthermore, electrodeposition as a simple synthesis route to test different Pt-alloys for the cathode catalyst in the fuel cell is explored by synthesis of PtNi and PtNiMo. The gas diffusion layer of the PEMFC is used as substrate to reduce the number of steps to form the membrane electrode assembly. In addition to cheaper and more durable materials, understanding of how the materials degrade, and how the degradation affects the other components is crucial to ensure a long lifetime. Finding reliable test methods to validate the lifetime of the final system is necessary to make fuel cell a trusted technology for vehicles, with predictable performance. In this work, commercial flow plates are studied, to see the effect of different load cycles and relative humidities on the corrosion of the plate. Defects originating from production is observed, and the effect of these defects on the corrosion is further analysed. Suggestions are given on how the design and production of bipolar plates should be made to reduce the risk of corrosion in the PEMFC. / Som en del av det globala arbetet med at reducera utsläppen av koldioxid måste alla fordon elektrifieras eller tankas med förnybart bränsle. Batterier har redan revolutionerat bilmarknaden, men bränsleceller är en viktig pusselbit för att också elektrifiera tunga fordon. Den typen av bränsleceller för fordon som finns tillgänglig på den kommersiella marknaden i dag är polymerelektrolytbränslecellen (PEMFC). För att PEMFC skall ta en större marknadsandel måste kostnaderna minskas och livslängden förlängas. PEMFC består av ett antal komponenter gjorda av olika material, bland annat polymer membran, ädelmetallkatalysator, och metalliska bipolära plattor. Kombinationen av olika material i tillägg till den höga temperaturen, hög fuktighet och låg pH gör att materialen i bränslecellen är utsatta för korrosion. Ädelmetallkatalysatorn är en av de kostdrivande komponenterna i bränslecellen. I denna studien presenteras en översikt över framstegen inom katalysatormaterial för PEM bränsleceller de senaste två åren. Sedan studeras elektroplätering som en enkel produktionsmetod för nanopartiklar av platina legeringar. Möjligheten att simultant plätera fler metaller, och att använda gasdiffutions-skiktet från bränslecellen som substrat för att reducera antal produktionsteg och därmed reducera kostnader, undersöks. Det möjliggör också snabb testning av olika legeringar för att identifiera den optimala sammansättningen med hög prestanda, lång livslängd och lite platina. I tillägg till att ta fram billigare och tåliga material är det viktigt att förstå hur materialen degraderar och hur degraderingen av ett material påverkar de andra komponenterna. Med den kunskapen kan man utveckla accelererade testmetoder för att bedöma livslängden av hela bränslecellen. Validerade testmetoder är viktigt för att styrka förtroendet till nya teknologier. I denna studien fokuseras det också på korrosion av bipolära plattor, och hur olika lastcykler och fuktnivåer som kan bli applicerad vid accelererad testning påverkar korrosionen. Också effekten av defekter från tillverkningen i den skyddande beläggningen analyseras med hänsyn till korrosion, för att ge mer insikt i hur bipolära plattor kan designas och produceras för att minska korrosionen.
234

Surface Distortion and Electrocatalysis : Structure-Activity Relationships for the Oxygen Reduction Reaction on PtNi/C Nanocatalysts / Distorsion de Surface et Electrocatalyse : Relations Structure-Activité pour la Réduction de l'Oxygène sur Nanocatalyseurs PtNi/C

Chattot, Raphaël 05 December 2017 (has links)
Cette thèse a été initialement motivée par la compréhension de l’activité électrocatalytique particulière de particules PtNi/C creuses pour l’electroréduction du dioxygène (ORR). L’étude des mécanismes de formation et croissance de ces particules creuses, grâce à des techniques operando basées sur l’interaction rayons X- et/ou électrons-matière, a permis de montrer que les défauts cristallins améliorent les propriétés électrocatalytiques de nanomatériaux bimétalliques pour l’ORR. Le concept de « catalyseur défectueux » a pu être progressivement étendu à d’autres nanostructures PtNi, notamment des nanocatalyseurs à forme contrôlée, grâce à de fructueuses collaborations avec d’autres laboratoires européens. Ce travail montre, qu’en raison de la distorsion de leur surface, les nanomatériaux défectueux présentent des propriétés de chimisorption uniques, définissant ainsi une nouvelle classe de catalyseurs prometteurs et stables. / This PhD thesis was initially motivated by the understanding of the peculiar electrocatalytic activity of hollow PtNi/C nanoparticles for the oxygen reduction reaction (ORR). Investigations on the formation and growth mechanism of this novel class of nanocatalysts using operando X-ray and electron-based techniques revealed that, beyond alloying effects, structural disorder is a lever to boost the ORR kinetics on bimetallic nanomaterials. The ‘defects do catalysis’ concept was progressively extended to various PtNi catalyst nanostructures, namely to advanced shape-controlled nanocatalysts from the ORR electrocatalysis landscape thanks to fruitful collaborations with European laboratories. This work shows that, through their distorted surface, microstrained nanomaterials feature unprecedented adsorption chemisorption properties and represent a viable approach to sustainably enhance the ORR activity.
235

Estimation of possibility to implement fuel cell technology for decentralized energy supply in Russia

Sveshnikova, Aleksandra January 2015 (has links)
Industrial power generation is an ever-changing practice. After the steam turbine was invented energy production developed with accelerated tempo. Coal replaced wood, oil replaced coal and after natural gas started being used as an energy source, no one could even imagine better and cleaner energy technologies. But in the 21st century renewable energy started its development. The western world decided to develop green, environmentally friendlier technologies with a strong desire to become independent form oil and gas exporters. Hydrogen energy and fuel cell technology are two of the most promising fields of energy study. The European Union and the USA regularly invest a lot of money for research in this area and rapidly develop an energy economy that is free from CO2 emissions. In this scientific report, the situation of hydrogen energy systems in the world but also with a large focus on Russia has been investigated. The main focus was made on successful international projects which have been created within last decades. Moreover, hydrogen production methods and fuel cell technology were described in detail. The cost to produce 1 kg of hydrogen gas based off of Russian economic figures and using water electrolysis and steam reforming process was estimated. Solid oxide and polymer electrolyte membrane fuel cells were considered in the analysis. The next step was to estimate effectiveness of combined technology with electrical power of 1 kW and economic feasibility of using such technology as stand-alone power generation system in the regions with decentralized electricity.
236

Versuchsaufbau zur Untersuchung des Shutdownprozesses von PEM-Brennstoffzellen unter Nutzung des Kathodenabgastaupunktes als Indikator für den Trocknungszustand des Stacks zur Vorbereitung von Kaltstarts

Pohl, Erik, von Unwerth, Thomas 27 May 2022 (has links)
Der Kaltstart von Polymerelektrolytmembran Brennstoffzellen (PEM-BZ) stellt nach wie vor eine wesentliche Herausforderung dar. Passende Betriebsstrategien sind für Start und Shutdown von entscheidender Bedeutung um den BZ-Stack nicht irreversibel zu schädigen. Vor allem das geeignete Wassermanagement muss in den Fokus gerückt werden, da gefrierendes Reaktionswasser sowohl beim Start als auch bei der Lagerung unter Frostbedingungen die Funktionstüchtigkeit der PEMBZ beeinträchtigen können. Im Rahmen des Forschungsprojektes HZwo: InTherm wurde von der Professur Alternative Fahrzeugantriebe ein Teststand für die Untersuchung von Shutdownprozeduren und Froststarts entwickelt. Für die Feuchtemessung wurde ein Taupunkthygrometer verwendet und um die Vorgänge im Stack nachzuvollziehen drei Stromdichte- Temperaturverteilungsmessungen integriert.
237

Production of platinum poor electrodes for PEMFC by electrochemical deposition

Werwein, Anton, Kunz, Karina, Reuber, Sebastian, Weiser, Mathias, Goldberg, Adrian, Partsch, Mareike, Michaelis, Alexander 27 May 2022 (has links)
A new R2R capable process to produce platinum-poor fuel cells was presented in the lab scale. Platinum particles were deposited electrochemically on a mesoporous carbon carrier with various carbon carriers (Super P Li, Denka Black Li 400, Denka Black Li 435, Ketjenblack EC300). FESEM images showed particles in the range of 50 nm one the electrode surface. The catalyst containing electrodes were transferred via hot press from different metallic and polymeric decal materials on a polymer exchange membrane. First functional membrane electrode assemblies show the proof-of-principles of this new process. / Ein neuer R2R-fähiger Prozess für die Herstellung platinumarmer Brennstoffzellen wurde im Labormaßstab etabliert. Platinumpartikel wurde elektrochemisch auf einen mesoporösen Kohlenstoffträger mit verschieden Leitrußen (Super P Li, Denka Black Li 400, Denka Black Li 435, Ketjenblack EC300) abgeschieden. FESEM-Aufnahmen zeigen Partikel in der Größenordnung von 50 nm auf der Elektrodenoberfläche. Die katalysatorhaltige Elektrode wird mittels eines Heißpressverfahren auf eine Polymeraustauschmembran übertragen. Erste funktionsfähige Membran-Elektroden-Assemblierungen zeigen die Funktionsfähigkeit des Prozesses.
238

Zielgrößen und Spannungsfelder beim Vergleich von Herstellungs-verfahren für metallische Bipolarplatten

Porstmann, Sebastian, Polster, Stefan, Reuther, Franz, Melzer, Sebastian, Nagel, Matthias, Psyk, Verena, Dix, Martin 27 May 2022 (has links)
Elektrochemische Energiewandler sind eine hervorragende Möglichkeit, die Energieversorgung der Zu-kunft zu sichern. Eine Schlüsselkomponente der hierfür benötigten Polymer-Elektrolyt-Membran-Brenn-stoffzellen und -Elektrolyseurzellen ist die Bipolarplatte. Für die Herstellung metallischer Bipolarplatten sind verschiedene umformende Fertigungstechnologien geeignet, die sich hinsichtlich erreichbarer Fer-tigungskosten, Endeigenschaften der Bipolarplatte und technologischer Prozessgrenzen unterschei-den. In diesem Artikel werden die aktuell präferierten Fertigungstechnologien wie die wirkmedienba-sierte Blechumformung, sowie das Hohlprägen und das Hohlprägewalzen zur Herstellung von metalli-schen Bipolarplatten miteinander verglichen und bewertet. / Electrochemical energy converters are an excellent option to secure the energy supply of the future. A key component of the polymer electrolyte membrane fuel cells and -electrolyser cells required for this purpose is the bipolar plate. Various forming technologies with different manufacturing costs, final prop-erties of the bipolar plates, and technological process limits are suitable for the fabrication of metallic bipolar plates. In this article, the currently preferred manufacturing technologies to produce metallic bipolar plates like precisely media-based sheet forming as well as hollow embossing and roll embossing, are compared and evaluated.
239

Application of Nanofibres in Polymer Composite Membranes for Direct Methanol Fuel Cells

Mollá Romano, Sergio 09 December 2015 (has links)
Tesis por compendio / [EN] Direct methanol fuel cells are feasible devices for efficient electrochemical power generation if some issues can be solved regarding both electrodes and membranes. The research carried out in this Ph.D. thesis has particularly focused on the concerns associated with the membranes. Nafion is the most standard fuel cell membrane material due to its high proton conductivity and exceptional chemical and mechanical stability. However, it suffers from a considerably high methanol permeability and a limited operating temperature (< 80 ºC). The first aspect was addressed with the use of PVA nanofibres and the second one replacing Nafion with SPEEK-based polymers. Composite membranes of Nafion with PVA nanofibres, surface functionalised with sulfonic acid groups, exhibited lower methanol permeabilities due to the intrinsic barrier property of PVA, although proton conductivity was also affected as a result of the non-conducting behaviour of the bulk PVA phase. Remarkably, the nanofibres provided strong mechanical reinforcement which enabled the preparation of low thickness membranes (< 20 micrometres) with reduced ohmic losses, thus counteracting their lower proton conductivities. SPEEK-based membranes were examined for DMFC operation within the intermediate temperature range of 80-140 ºC, in which sluggish electrochemical reactions at the electrodes are accelerated and proton conductivity activated. SPEEK was blended and crosslinked with PVA and PVB polymers for avoiding its dissolution in hot water conditions. SPEEK-PVA compositions showed practical proton conductivities and SPEEK-PVB blends presented very low methanol permeabilities. Nanocomposite membranes composed of SPEEK-30%PVB nanofibres embedded in a SPEEK-35%PVA matrix were prepared and characterised. A nanocomposite membrane crosslinked at 120 ºC revealed promising results for DMFCs operating at intermediate temperatures. Electrospinning is concluded to be a suitable technique for obtaining polymer nanofibre mats intended for advanced composite membranes with improved characteristics and fuel cell performances. / [ES] Las pilas de combustible de metanol directo son dispositivos factibles para la generación electroquímica eficiente de energía eléctrica si se pueden solucionar algunas cuestiones relacionadas tanto con los electrodos como las membranas. La investigación llevada a cabo en esta tesis doctoral se ha centrado particularmente en los problemas asociados con las membranas. Nafion es el material de membrana más común para pilas de combustible debido a su alta conductividad protónica y excepcional estabilidad química y mecánica. Sin embargo, padece una considerablemente alta permeabilidad al metanol y una limitada temperatura de operación (< 80 ºC). El primer aspecto se abordó con el uso de nanofibras de PVA y el segundo reemplazando Nafion con polímeros basados en SPEEK. Membranas compuestas de Nafion con nanofibras de PVA, funcionalizadas en su superficie con grupos ácidos sulfónicos, exhibieron menores permeabilidades al metanol debido a la propiedad barrera intrínseca del PVA, aunque la conductividad protónica también se vio afectada como resultado del comportamiento global no conductor de la fase de PVA. Remarcablemente, las nanofibras proporcionaron un refuerzo mecánico fuerte que permitió la preparación de membranas de bajo espesor (< 20 micrómetros) con unas pérdidas óhmicas reducidas, así contrarrestando sus menores conductividades protónicas. Se examinaron membranas basadas en SPEEK para la operación de pilas de combustible de metanol directo dentro del rango intermedio de temperaturas entre 80-140 ºC, en el que las lentas reacciones electroquímicas en los electrodos se aceleran y la conductividad protónica se activa. El SPEEK se combinó y entrecruzó con los polímeros de PVA y PVB para evitar su disolución en condiciones de agua caliente. Las composiciones de SPEEK-PVA mostraron conductividades protónicas funcionales y las mezclas de SPEEK-PVB presentaron permeabilidades al metanol muy bajas. Se prepararon y caracterizaron membranas nanocompuestas constituidas por nanofibras de SPEEK-30%PVB embebidas en una matriz de SPEEK-35%PVA. Una membrana nanocompuesta entrecruzada a 120 ºC reveló resultados prometedores para pilas de combustible de metanol directo operando a temperaturas intermedias. Se puede concluir que la electrohilatura es una técnica apropiada para la obtención de mallas de nanofibras poliméricas destinadas a membranas compuestas avanzadas con características y rendimientos en pilas de combustible mejorados. / [CA] Les piles de combustible de metanol directe són dispositius factibles per a la generació electroquímica eficient d'energia elèctrica si es poden solucionar algunes qüestions relacionades tant amb els elèctrodes com les membranes. La investigació duta a terme en esta tesi doctoral s'ha centrat particularment en els problemes associats amb les membranes. Nafion és el material de membrana més comú per a piles de combustible a causa de la seua alta conductivitat protònica i excepcional estabilitat química i mecànica. No obstant això, patix una considerablement alta permeabilitat al metanol i una limitada temperatura d'operació (< 80 ºC). El primer aspecte es va abordar amb l'ús de nanofibres de PVA i el segon reemplaçant Nafion amb polímers basats en SPEEK. Membranes compostes de Nafion amb nanofibres de PVA, funcionalizades en la seua superfície amb grups àcids sulfónics, van exhibir menors permeabilitats al metanol a causa de la propietat barrera intrínseca del PVA, encara que la conductivitat protònica també es va veure afectada com resultat del comportament global no conductor de la fase de PVA. Remarcablement, les nanofibres van proporcionar un reforç mecànic fort que va permetre la preparació de membranes de baixa grossària (< 20 micròmetres) amb unes pèrdues òhmiques reduïdes, així contrarestant les seues menors conductivitats protòniques. Es van examinar membranes basades en SPEEK per a l'operació de piles de combustible de metanol directe dins del rang intermedi de temperatures entre 80-140 ºC, en el que les lentes reaccions electroquímiques en els elèctrodes s'acceleren i la conductivitat protònica s'activa. El SPEEK es va combinar i va entrecreuar amb els polímers de PVA i PVB per a evitar la seua dissolució en condicions d'aigua calenta. Les composicions de SPEEK-PVA van mostrar conductivitats protòniques funcionals i les mescles de SPEEK-PVB van presentar permeabilitats al metanol molt baixes. Es van preparar i caracteritzar membranes nanocompostes constituïdes per nanofibres de SPEEK-30%PVB embegudes en una matriu de SPEEK-35%PVA. Una membrana nanocomposta entrecreuada a 120 ºC va revelar resultats prometedors per a piles de combustible de metanol directe operand a temperatures intermèdies. Es pot concloure que l'electrofilatura és una tècnica apropiada per a l'obtenció de malles de nanofibres polimériques destinades a membranes compostes avançades amb característiques i rendiments en piles de combustible millorats. / Mollá Romano, S. (2015). Application of Nanofibres in Polymer Composite Membranes for Direct Methanol Fuel Cells [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/58611 / TESIS / Premios Extraordinarios de tesis doctorales / Compendio
240

Model on degradation of PEM fuel cells in marine applications / Modell för degradering av PEM-bränsleceller för marina applikationer

Östling, Erik January 2021 (has links)
Sjöfarten står för 3 % av världens totala växthusgaser och är idag högst beroende av fossila bränslen. Ett alternativ för att gå över till en fossilfri flotta är användning av bränsleceller och vätgas som drivmedel. Om vätgasen produceras från elektrolys med förnyelsebara energikällor så är driften utsläppsfri och koldioxidneutral. Bränsleceller kan användas i många olika sammanhang, men har ännu inte slagit igenom med full kraft. En anledning till detta är livslängden som är för kort. För att sjöfarten ska kunna implementera bränslecellsdrift behöver nedbrytningen av bränslecellen bli vidare utforskad och motverkad. Syftet med detta examensarbete var att hitta de mest signifikanta nedbrytningsmekanismerna för sjöfarten samt att bygga en modell för att förutspå livslängden utifrån lastprofiler från fartyg.  Rapportens avgränsningar var att enbart studera PEM-bränsleceller tack vare dess höga energitäthet och att teknologin är närmast marknaden för mobila applikationer. En litteraturstudie genomfördes för att fastställa de viktigaste nedbrytningsmekanismerna samt de faktorer som begränsar livslängden. Dessa bestämdes till start/stop cykler samt lastcykler vilka försämrar konduktiviteten i membranet samt minskar den elektrokemiska ytarean. En empirisk modell från experiment från litteraturen etablerades för att hitta relationen mellan parametrarna konduktivitet och elektrokemisk ytarea som funktion av start/stop cykler respektive lastcykler. En Comsol-modell användes för att utvärdera bränslecellens prestanda med dessa försämrade parametrar. Två lastprofiler analyserades och tolkades som antal start/stop cykler samt lastcykler för att utvärdera prestandan som funktion av antal år i drift. Båda fallen var i drift till dess att prestandan minskat med 20 % utvärderat vid strömtätheten 0.6 A/cm2. Båda lastprofilerna var utvärdera med olika körstrategier för att jämföra den modellerade livslängden beroende på ingångsvärden. Den första lastprofilen delades in i Case 1a och Case 1b där antalet start/stop cykler och lastcykler varierade. Resultatet visade att antalet timmar i drift mer än tredubblades i Case 1b där båda ingående indata hade minskats.   Case 2 delades upp i tre olika körstrategier där Case 2a var en referens som jämfördes mot Case 2b respektive Case 2c. Skillnaden mot Case 2b var att antalet start/stop cykler per dag multiplicerades med faktor 4. Resultatet från modellen var att livstiden minskade från 6 till 4 år. Vidare utvärderades Case 2c där istället antalet lastcykler dividerades med faktor 4, allt annat identiskt med Case 2a. Utfallet var en ökad livslängd från 6 år till 11 år, med totalt 32 032 timmar i drift. Denna livslängd kan jämföras med kommersialiserade marina produkter från Ballard och Powercell, där livslängden är 30 000 respektive 20 000 timmar i drift.  Sammanfattningsvis kan det konstateras att både start/stop cykler och lastcykler bryter ner bränslecellen och därmed minskar dess prestanda. Lastcykler var den faktor som var mest förödande gällande livslängden. Den modellerade livslängden på 32 032 timmar indikerar att den empirisk modellen tillsammans med Comsol-modellen genererade realistiska resultat. Slutligen kan sägas att ett område för framtida forskning inom ämnet innefattar lastcykler eftersom denna hade störst påverkan på modellen. Att särskilja olika typer av lastcykler och koppla till olika degradering skulle skapa än mer förståelse för livslängden. Då denna studie genomfördes på bränslecellsnivå skulle framtida studier kunna inkludera att analysera degradering på systemnivå för att få mer insikt i dessa processer. / The shipping industry emits 3 % of the global GHG-emissions and is highly dependent on fossil fuels. One alternative to decarbonise the sector is by utilising hydrogen in fuel cells. The propulsion is free from emissions if hydrogen is produced from renewables. The fuel cell technology can be applied in various applications but have not been fully commercialised. One of the biggest bottlenecks for fuel cell technology is the durability that needs to be improved. In order for marine vessels to implement hydrogen propulsion, the degradation need to be further understood and mitigated. The purpose of this thesis was to assess the most significant degradation mechanisms for marine applications and to build a model to evaluate the lifetime depending on load profiles. The scope of the thesis was to include PEMFCs since they have the highest power density and are closest to commercialisation for transport applications. A literature review was conducted to assess the most important degradation mechanisms and operating conditions that limits the lifetime, which concluded in start/stop cycling and load cycling. These conditions deteriorate the membrane conductivity and the electrochemical surface area. An empirical model based on experimental data from the literature was conducted to find relationships for conductivity and ECSA as function of start/stop cycling and load cycling, respectively. A Comsol model was established to evaluate performance reduction with degraded parameters. Two different load cycles were interpreted as number of start/stop cycles and load cycles in order to simulate the degradation. The output was polarization curves as function of operating years. Each case was operated until a performance reduction of 20 % was obtained at the current density of 0.6 A/cm2.  Both load profiles were analysed with different operation strategies to compare the resulting lifetime. The first load curve was divided into Case 1a and Case 1b where start/stop cycles and load cycles were altered. The results showed that the lifetime in operation hours was more than three-folded in Case 1b when the number of start/stop cycles and load cycles was reduced.  Case 2 was divided into three operating strategies. For comparison with Case 2a, the number of start/stop cycles per day in Case 2b was increased by a factor of 4. The result was that the lifetime declined from 6 to 4 years. Furthermore, Case 2c evaluated the lifetime if the number of load cycles per day decreased by a factor of 4, all else being equal to Case 2a. The outcome was an increment in lifetime from 6 to 11 years, with a total of 32 032 hours of operation. This lifetime can be compared to commercialised products from Ballard and Powercell with lifetimes of 30 000 and 20 000 operating hours, respectively. Conclusively, the simulations showed that both start/stop cycling and load cycling deteriorates the fuel cell performance. Load cycling is the operating condition that cause the most severe degradation. Moreover, the modelled lifetime of 32 032 hours indicates that the empirical model in combination with the Comsol model generate realistic lifetimes. Finally, since load cycling had the most vital impact on the lifetime, one of the topics for future research would be to distinguish different types of load cycles and connect to separate degradation outcomes. Since the model was on fuel cell level, future work could also include systems effects such as ripple current or distributions within fuel cell stacks.

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