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

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

As foodstuffs are being produced, transported and stored in greater quantities than ever before in human history and with an alarming amount of food products being lost to spoilage every year, new, environmentally friendly ways of preserving food products are being actively researched and developed in today’s world. Oxygen is a key pathway towards food decay and destruction, due to its dual roles as a source of respiration for the multitude of microorganisms that can cause food spoilage and through direct destruction through oxidation reactions within food products that cause oxidative deterioration. Fuel cells have the theoretical potential to be an energy efficient and environmentally friendly way of preserving food, such as fish, fruit and vegetables.  Because of their nature to consume oxygen through the electrochemical reactions that produces their electrical power, they have the potential to be used to reduce localised oxygen content for the storage and transportation of foods, minimising their spoilage, as well as potentially providing electrical energy for other components in potential control systems for the fuel cell. The purpose of this project is to design and build a PEM fuel cell and examine its potential for lowering of oxygen concentrations at the gas output at the cathode.  The outcome of these experiments are designed to validate the  theoretical capacity of fuel cells to reduce output oxygen concentrations to levels that are able to aid in the preservation of foodstuffs.  It is hoped that this study, in conjunction with the researched literature, can be used as a guide for future food shipping and storage methods. The experimental stage of this diploma work was unsatisfactory. The fuel cell was unable to produce a voltage and the reactant gases were unable to flow through the fuel cell due to a design flaw. Therefore the effectiveness of a fuel cell for depletion of oxygen to levels able to preserve food is based on the theoretical basis of the internal PEM fuel cell reactions, as well as studying past literature and patents. If the theoretical ability of the fuel cell is proven, it can be asserted that PEM fuel cells have the potential to be a real contender in the field of food preservation in shipping and storage, as well as offering greater levels of control for supplies for how and when they can ship their product. However this will require more independent research development work on the effects of low oxygen concentrations on a fuel cell operation as well as the preservation effects on a greater variety of foodstuffs. Furthermore, more research is required for more efficient and cheaper fuel cell catalysts or innovative designs are required to avoid concentration losses that arise from oxygen reduction at low oxygen levels.

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

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

[ES] Las pilas de combustibles son dispositivos de un coste elevado y frágiles ante ambientes contaminados o condiciones inadecuadas de operación como: temperaturas extremas o mala gestión del agua producida como residuo de la pila. Para mejorar la fiabilidad de una pila de combustible es necesario diagnosticar de una manera oportuna los fallos y así evitar daños que reduzcan el desempeño del módulo o que lo inhabiliten. Este trabajo busca contribuir al mejoramiento de la fiabilidad de las pilas de combustible de baja temperatura y de esta forma favorecer el uso de hidrógeno en la transición a una energía descarbonizada. Para lograrlo, se realizaron tres actividades principales: modelado de una pila de hidrógeno, ajuste paramétrico del modelo desarrollado y, por último, aplicación de técnicas de diagnóstico de fallos basados en modelos. En el laboratorio de Recursos Energéticos Renovables Distribuidos LabDER de la Universitat Politècnica de València, se estudia el desempeño de sistemas híbridos renovables, incluyendo una línea de hidrógeno, desde la producción, almacenamiento y reconversión en electricidad en una pila de combustible, por tanto, se ha podido validar el modelo. En un primer momento se identificó la necesidad de un modelo que emplee la temperatura como señal de salida y que retroalimente el sistema, y que tuviese en cuenta señales propias del módulo comercial; sin embargo, el uso de la temperatura como señal y la no linealidad de las ecuaciones físicas, químicas, eléctricas y empleadas, generan un modelo altamente complejo. El ajuste paramétrico del modelo se realizó empleando algoritmos de optimización. Tomando como base al algoritmo de Enjambre de Partículas, se desarrolló una nueva propuesta llamada Scout GA, este algoritmo fue utilizado en otras aplicaciones y pruebas de convergencia para verificar su desempeño frente al fenómeno de estancamiento prematuro y logrando mejorar la precisión y velocidad de convergencia de otras propuestas. Como resultado de la validación de este modelo, en una primera simulación usando datos reales de funcionamiento correspondientes a 1500 segundos, el error de simulación fue del 2,21% en la señal de tensión y del 1,97% en la señal de temperatura, obteniendo un error medio del 2,09%. En un segundo conjunto de datos de algo más de 2.500 segundos de funcionamiento, el error de simulación fue del 2,40% y del 1,96% para las señales de tensión y temperatura, respectivamente. Se estima que el error medio de simulación para ambas señales y condiciones de funcionamiento similares es inferior al 2,5%. Buscando mejorar la fiabilidad de la pila, se realizó el trabajo de diagnóstico de fallos, este partió de la simulación de fallos, mediante la modificación de algunas señales de entrada del modelo, los fallos se caracterizaron mediante el tratamiento estadístico de 12 residuos, obteniendo firmas de fallos, que, en su conjunto, formaron una matriz de fallos. Luego, un algoritmo de diagnóstico propuesto permitió identificar y aislar 14 fallos. permitiendo concluir que, el modelo predice eficazmente los fallos de las pilas PEMFC y podría extrapolarse a otras pilas de combustible. / [CA] Les piles de combustibles són dispositius d'un cost elevat i fràgils davant ambients contaminats o condicions inadequades d'operació com: temperatures extremes o dolenta gestió de l'aigua produïda com a residu de la pila. Per a millorar la fiabilitat d'una pila de combustible és necessari diagnosticar d'una manera oportuna les fallades i així evitar danys que reduïsquen l'acompliment del mòdul o que l'inhabiliten. Este treball busca contribuir al millorament de la fiabilitat de les piles de combustible de baixa temperatura i d'esta manera afavorir l'ús d'hidrogen en la transició a una energia *descarbonizada. Per a aconseguir-ho, es van realitzar tres activitats principals: modelatge d'una pila d'hidrogen, ajust paramètric del model desenvolupat i, finalment, aplicació de tècniques de diagnòstic de fallades basades en models. En el laboratori de Recursos Energètics Renovables Distribuïts *LabDER de la Universitat Politècnica de València, s'estudia l'acompliment de sistemes híbrids renovables, incloent-hi una línia d'hidrogen, des de la producció, emmagatzematge i reconversió en electricitat en una pila de combustible, per tant, s'ha pogut validar el model. En un primer moment es va identificar la necessitat d'un model que empre la temperatura com a senyal d'eixida i que retroalimente el sistema, i que tinguera en compte senyals propis del mòdul comercial, no obstant això, l'ús de la temperatura i la no linealitat de les equacions físiques, químiques, elèctriques i tèrmiques empleades, deriven en un model altament complex. L'ajust paramètric del model de pila de combustible es va realitzar emprant algorismes d'optimització. Prenent com a base a l'algorisme d'Eixam de Partícules, es va desenvolupar una nova proposta anomenada Scout GA, aquest algorisme va ser utilitzat en altres aplicacions i proves de convergència per a verificar el seu acompliment enfront del fenomen d'estancament prematur i aconseguint millorar la precisió i velocitat de convergència d'altres propostes. La simulació i identificació del model té un cost computacional entre 7 i 20 ms per iteració, on es van aconseguir errors de simulació menors al 2.5% Com a resultat de la validació d'aquest model, en una primera simulació usant dades reals de funcionament corresponents a 1500 segons, l'error de simulació va ser del 2,21% en el senyal de tensió, del 1,97% en el senyal de temperatura i un error mitjà del 2,09%. En un segon conjunt de dades d'una mica més de 2.500 segons de funcionament, l'error de simulació va ser del 2,40% i del 1,96% per als senyals de tensió i temperatura, respectivament. S'estima que l'error mitjà de simulació per a tots dos senyals i condicions de funcionament similars és inferior al 2,5%. Buscant millorar la fiabilitat de la pila, es va fer el treball de diagnòstic de fallades, aquest va partir de la simulació de fallades, mitjançant la modificació d'alguns senyals d'entrada del model, les fallades es van caracteritzar mitjançant el tractament estadístic de 12 residus, obtenint signatures de fallades, que en el seu conjunt, van formar una matriu de fallades. després un algorisme de diagnòstic proposat, va permetre identificar i aïllar 14 fallades. Permetent concloure que, el model prediu eficaçment les fallades de les piles PEMFC i podria extrapolar-se a altres piles de combustible. / [EN] Fuel cells are high-cost devices that are fragile in contaminated environments or in inadequate operating conditions, such as extreme temperatures or poor water management, produced as battery waste. To improve the reliability of a fuel cell, it is necessary to diagnose failures promptly and thus avoid damage that reduces the module's performance or disables it. This work seeks to contribute to improving the reliability of low-temperature fuel cells and thus promote the use of hydrogen in the transition to decarbonized energy. To achieve this, three main activities were carried out: modeling a hydrogen fuel cell, parametric adjustment of the developed model, and application of model-based fault diagnosis techniques. In the LabDER Distributed Renewable Energy Resources laboratory of the Polytechnic University of Valencia, the performance of renewable hybrid systems is studied, including a hydrogen line, from production, storage, and reconversion into electricity in a fuel cell, therefore, has been able to validate the model. Initially, a fuel cell model that uses temperature as an in/output signal is required. Also, the model must be able to use the reals signals supplied for the commercial module. However, using temperature and an equation set that includes the non-linearity of the physical, chemical, electrical, and thermal equations resulted in a highly complex model. The parametric adjustment of the fuel cell model was performed using optimization algorithms. Based on the Particle Swarm algorithm, a new proposal called Scout GA was developed. This algorithm was used in other applications and convergence tests to verify its performance against the premature stagnation phenomenon and improved the accuracy and speed of convergence of other proposals. The simulation and identification of the model have a computational cost between 7 and 20 ms per iteration, where simulation errors of less than 2.5% were achieved. As a result of the validation of this model, in a first simulation using real operating data corresponding to 1,500 seconds, the simulation error was 2.21% for the voltage signal, 1.97% for the temperature signal, and an average error of 2.09%. In a second data set for slightly more than 2500 seconds of operation, the simulation error was 2.40% and 1.96% for the voltage and temperature signals, respectively. The average simulation error for both signals and similar operating conditions is estimated to be less than 2.5%. To improve the reliability of the stack, the fault diagnosis work was carried out, starting from the simulation of faults by modifying some input signals of the model; the faults were characterized by the statistical treatment of 12 residuals, obtaining fault signatures, which formed a fault matrix. Then, a proposed diagnostic algorithm allowed to identify and isolate 14 faults. Allowing to conclude that the model effectively predicts the PEMFC stack faults and could be extrapolated to other fuel cells. / Ariza Chacón, HE. (2024). Contribuciones al modelado y diagnóstico de fallos en PEMFC para mejorar la fiabilidad en sistemas híbridos renovables [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/203614

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 importants. / Perfluorinated 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.

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

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

Thesis (M. Tech. - (Engineering: Electrical, Department: Electronic Engineering, Faculty of Engineering and Technology))--Vaal University of Technology. / Industrial countries, such as South Africa, rely heavily on energy sources to function profitably in today’s economy. Based on the 2008 fossil fuel CO2 emissions South Africa was rated the 13th largest emitting country and also the largest emitting country on the continent of Africa, and is still increasing. It was found that fuel cells can be used to generate electricity and that hydrogen is a promising fuel source. A fuel cell is an energy generation device that uses pure hydrogen (99.999%) and oxygen as a fuel to produce electric power. A regenerative fuel cell is a fuel cell that runs in reverse mode, which consumes electricity and water to produce hydrogen. This research was aimed at designing and constructing an optimised control system to control the hydrogen pressure in a proton exchange membrane regenerative fuel cell. The hydrogen generated by the fuel cell must be stored in order to be used at a later stage to produce electricity. A control system has been designed and constructed to optimise the hydrogen pressure control in a regenerative proton exchange membrane fuel cell. An experiment that was done to optimise the hydrogen system included the effects that the cathode chamber pressure has on the production of hydrogen and the most effective method of supplying hydrogen to a storage tank. The experiment also included the effects of a hydrogen buffer tank on the output hydrogen pressure and if the system can accommodate different output pressures. It was found that the cathode chamber pressure doesn’t need to be controlled because it has no effect on the rate of hydrogen produced. The results also showed that the flow of hydrogen need not to be controlled to be stored in a hydrogen storage tank, the best method is to let the produced hydrogen flow freely into the tank. The hydrogen produced was also confirmed to be 99.999% pure. The system was also tested at different output pressures; the control system successfully regulated these different output pressures.