Thesis (M. Sc. (Chemistry)) -- University of Limpopo, 2017. / In order to meet the great demand of energy supply globally, there must be a transition from dependency on fossil fuel as a primary energy source to renewable source. This can be attained by use of hydrogen gas as an energy carrier. In the context of hydrogen fuel cell economy, an effective hydrogen generation is of crucial significant. Hydrogen gas can be produced from different methods such as steam reforming of fossil fuels which emit greenhouse gases during production and from readily available and renewable resources in the process of water electrolysis. Hydrogen generated from water splitting using solar energy (photocatalysis) or electric energy (electrocatalysis) has attracted most researchers recently due to clean hydrogen (without emission of greenhouse gases) attained during hydrogen production. In comparison with photocatalytic water splitting directly using solar energy, which is ideal but the relevant technologies are not yet commercialized, electrolysis of water using catalyst is more practical at the current stage. The platinum group noble metals (PGMs) are the most effecting electrocatalysts for hydrogen evolution reactions (HER) but their scarcity and high cost limit their application. In this study, we presented the noble metal free organic-inorganic hybrid composites and their HER electrocatalysis performances were investigated. Polyaniline-metal organic framework (PANI/MOF) composite was prepared by chemical oxidation of aniline monomer in the presence of MOF content for hydrogen production. The properties of PANI, MOF and PANI/MOF composite were characterised for their structure and properties by X-ray diffraction (XRD), field-emission scanning electron microscopy (SEM), Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), Raman, transmission electron microscopy (TEM), ultraviolet-visible spectroscopy (UV-vis), atomic absorption spectroscopy (AAS), square wave (SWV) and cyclic voltammetry (CV). There was a clear interaction of MOF on the backbone of the PANI matrix through electrostatic interaction as investigated by both Raman and FTIR. The MOF exhibited irregular crystals with further wrapping of MOF by PANI matrix as evidenced by both SEM and TEM analyses. The PANI composite exhibited some nanorods and microporous structure. x The determined energy band gap of the composite was in good agreement with previously reported catalysts for hydrogen evolution reaction (HER). The thermal stability of PANI increased upon addition of MOF. Experiments probing the electrochemical, HER and photophysical properties revealed that the composite was very stable and robust with significant improvement in properties. The resulting composite is a promising low-cost and environmentally friendly hydrogen production material. In this work we also reported about novel poly (3-aminobenzoic acid)-metal organic framework referred as PABA/MOF composite. Spectroscopic characterisations (UV-vis and FTIR) with support of XRD and TGA revealed a successful interaction between PABA and MOF. Morphological characterisation established that PABA is wrapping MOF and the amorphous nature of the materials were not affected. The catalytic effect of PABA and PABA/MOF composites on HER was studied using exchange current density and charge transfer coefficient determined by the Tafel slope method. A drastic increase in catalytic H2 evolution was observed in PABA and composite. Moreover, they merely require overpotentials as low as ~-0.405 V to attain current densities of ~0.8 and 1.5 Am-2 and show good longterm stability. We further demonstrated in the work the electrocatalytic hydrogen evolution reaction of MOF decorated with PABA. These novel MOF/PABA composites with different PABA loading were synthesised via in situ solvothermal synthesis of MOF in the presence of PABA. It was deduced that PABA with different loading amount have an influence on the morphologies, optical properties and thermal stabilities of MOF. Interestingly, the MOF/PABA composites exhibited the great significant on the HER performance and this is potentially useful in HER application for hydrogen fuel cell. / Sasol Inzalo foundation and National Research Foundation of South Africa

With the growing demand for electricity, renewable sources of energy have garnered a lot of support from all quarters. The problem with depending on these renewable sources is that the output from them is independent of the demand. Storage of electricity gives us an opportunity to effectively manage and balance the supply and demand of electricity. Fuel cells are a fast developing and market capturing technology that presents efficient means of storing electricity in the form of hydrogen. The aim of this research is to study the impact of integrating hydrogen fuel cell storage system with a wind farm to improve the reliability of the grid for allowing higher penetration of renewable energy sources in the power system. The installation of energy storage systems strongly depends on the economic viability of the storage system. We identified four types of fuel cells that could be used in a hydrogen fuel cell storage system. We bring together a range of estimates for each of the fuel cell systems for the economic analysis that is targeted towards the total capital costs and the total annualized costs for the storage system for individual applications like rapid reserve and load shifting. We performed sensitivity analysis to determine the effect of varying the rate of interest and cost of fuel cell on the total annualized cost of the storage system. Finally, we compared the costs of hydrogen based storage system with other storage technologies like flywheel, pumped hydro, CAES and batteries for the individual application cases.

Solid-state nuclear magnetic resonance (ssNMR) spectroscopy was used to anal- yse numerous graphene-sheet based materials in an attempt to study their effects on the performance of polymer electrolyte membrane fuel cell (PEM-FC) mate- rials. It has been noted in the literature that fuel cells which incorporated these materials (e.g. functionalized graphene, doped carbon nanotubes (CNTs), etc.) displayed increased performance over a wider range of environmental conditions, chiefly temperature and relative humidity. The inter-material interactions behind this phenomenon are poorly described at best. Due to its extreme site speci ficity and sensitivity to minute differences in nuclear electromagnetic environments, ss- NMR is an ideal tool for investigating the complicated interactions at work in these systems. While the electronically conductive, amorphous, non-stoichiometric, and low spin-density nature of these materials presented challenges to the collection of NMR spectra, the results presented here display the remarkable utility of this method in the study of analogues and derivatives of graphene. Graphene Oxide (GO), a derivative of graphene, has intrinsic proton conduc- tivity which is similar to Na fon, the most popular proton exchange membrane material currently used in fuel cells. Research into acid-functionalized graphene oxides and determining the role of acidic groups in increasing proton conductivity will help to improve polymer electrolyte membrane performance in fuel cell sys- tems. Multinuclear solid-state NMR (ssNMR) spectroscopy was used to analyse the structure and dynamics of GO and a number of sulfonic acid derivatives of GO, both novel and previously reported. 13C spectra showed the disappearance of surface-based oxygen groups upon GO functionalization, and can be used to identify linker group carbon sites in previously synthesized and novel functional- ized GO samples with high speci city. Dehydration of these samples allows the collection of 1H spectra with resolved acidic proton and water peaks. The effect of dehydration on the proton spectrum is partially reversible through rehydration. Deuteration of the acidic groups in high temperature and acidic conditions was virtually unsuccessful, indicating that only the surface and not the intercalated functional groups play a role in the enhanced proton conductivity of ionomer / functionalized GO composites. Increased surface area and increased delamination of functionalized GO is suggested to be important to improved PEM-FC perfor- mance. This synthesis and method of analysis proves the utility of ssNMR in the study of structure and dynamics in industrially relevant amorphous carbon ma- terials, despite the obvious di culties caused by naturally broad signals and low sensitivity. Graphene and carbon nanotubes (CNTs) have been investigated closely in re- cent years due to their apparent positive effect on the electrochemical performance of new fuel cell and battery systems as catalyst stabilizers, supports, or as metal- free catalysts. This is particularly true for doped graphene and CNTs, where only a small amount of doping with nitrogen and/or phosphorus can have a re- markable effect on materials performance. A direct link between structure and function in these materials is, as of yet, unclear. Doped graphene and CNTs were synthesized using varied chemical vapour deposition (CVD)-based methods, and ssNMR was used to unambiguously identify dopant atom sites, revealing that these particular synthesis methods result in highly homogeneous populations of installed phosphorus and nitrogen atoms. We present the first experimental 15N spectrum for graphitic nitrogen in N-doped graphene. 15N-labeled nitrogen doped graphene synthesized as reported here produces mainly graphitic nitrogen sites located on the edges of sheets and around defect sites. 1H-1H and 1H-15N corre- lations were also used to probe dopant nitrogen sites in labelled and unlabelled N-doped graphene. A nearly homogeneous population of phosphorus in P-doped graphene is found, with an overwhelming majority of graphitic phosphorus and a small amount of phosphate oligomer. Similar findings are noted for the phos- phorus sites in phosphorus and nitrogen co-doped CNTs with a minor change in chemical shift, as would be expected from two chemically similar phosphorus sites in carbon allotropes (CNTs versus graphene sheets) with signifi cantly different electronic structures. Ionomeric sulfonated polyether ether ketone (SPEEK) membranes were doped with functionalized graphenes, and the proton conductivities of these composite membranes was measured at fuel cell operational temperatures and percent relative humidities (%RH). The differences in proton conductivity between pure SPEEK membranes and composites with different dopants and doping levels at varied conditions were investigated through high-fi eld 1H ssNMR. It was found that high- speed MAS was able to dehydrate membranes under water-saturated conditions, and so lower %RH conditions were better able to produce reliable ssNMR results. The addition of graphitic dopants appeared to have an overall detrimental effect on the bulk proton conductivity of membranes, while concurrently these doped membranes had a broadened operational temperature window. In an attempt to explore the positive influence of nitrogen doping on the effec- tive lifetime of carbon-supported platinum catalysts used in automotive hydrogen fuel cell systems, solid-state NMR was employed to probe the difference (if any) between doped catalyst supports made from different carbon and nitrogen sources. 1H spectroscopy showed a variety of sites present in the doped samples; some likely from residual starting material but others from novel sites within the doped cat- alyst supports. Double-quantum and 2D 1H experiments were used to examine the structure of these catalysts, while 13C CPMG experiments (see Chapter 2) revealed subtle differences in the nuclear relaxation rates of these materials, poten- tially related to their electronic conductivity. The results of the ssNMR analysis were insuffcient to provide an unambiguous picture of the dopant sites within these carbon black samples; this was due in equal parts to the lack of isotopically labelled dopants, the effects of electronic induction and ring current shifts on data acquisition and analysis, and the broad array of different 13C chemical shift en- vironments present in the carbon black itself. While the data is still interesting spectroscopically, suggestions are made at the end of this chapter to expand upon the lessons learned through this study to produce more useful results from similar samples in the future. / Thesis / Doctor of Philosophy (PhD) / Solid-state nuclear magnetic resonance (ssNMR) spectroscopy was used to anal- yse numerous graphene-sheet based materials in an attempt to study their effects on the performance of polymer electrolyte membrane fuel cell (PEM-FC) materials. It has been noted in the literature that fuel cells which incorporated these materials (e.g. functionalized graphene / graphite, doped carbon nanotubes (CNTs), etc.) displayed increased performance over a wider range of environmental conditions, chiefly temperature and relative humidity. The inter-material interactions behind this phenomenon are poorly described at best. Due to its extreme site specifi city and sensitivity to minute differences in nuclear electromagnetic environments, ss- NMR is an ideal tool for investigating the complicated interactions at work in these systems. While the electronically conductive, amorphous, non-stoichiometric, and low spin-density nature of these materials presented challenges to the collection of NMR spectra, the results presented here display the remarkable utility of this method in the study of analogues and derivatives of graphene. Covalently functionalized graphene / graphite was synthesized, and the struc- tures of several derivatives were recorded with remarkable resolution, such that functional group carbons were resolvable. The proton dynamics of this material were remarkably slow, and so improvements in composite PEM ion conductiv- ity were proposed to be caused by surface interactions between dopant and poly- mer. The proton dynamics of ionomer graphene composites were also investigated through ssNMR. A number of graphene and CNT samples doped with phosphorus and 15N-labelled nitrogen were also analysed, and the synthesis methods employed were found to produce chemically homogeneous dopant sites with few by-products. Absent isotopic labelling, nitrogen dopant sites in carbon black samples were found to affect the relaxation properties of protons within nitrogen doped carbon black.

Στην παρούσα διπλωματική παρουσιάστηκαν όλα τα θεωρητικά και τεχνικά στοιχεία των κελιών καυσίμου. Επίσης, έγινε ανάλυση των διαθέσιμων τεχνολογιών των κελιών καυσίμου, καθώς και μια ιστορική αναδρομή. Τα κελιά καυσίμου και ειδικότερα το υδρογόνο σαν καύσιμο αναμένεται να διαδραματίσει τον σημαντικότερο ρόλο τις επόμενες δεκαετίες. Η τεχνολογία των κελιών καυσίμου συνεχώς βελτιώνεται. Τα κελιά καυσίμου βρίσκουν ολοένα και μεγαλύτερο εύρος εφαρμογών, καθώς είναι ιδιαίτερα φιλικά προς το περιβάλλον. Η αρχή λειτουργίας τους είναι από πολύ παλιά γνωστή, στους επιστημονικούς κύκλους. Το πρόβλημα ήταν ανέκαθεν η βελτιστοποίηση των συστημάτων, ώστε να γίνουν οικονομικότερα και πιο αποδοτικά. Η τεχνολογία της κυψέλης καυσίμου και της μετατροπής του υδρογόνου σε ηλεκτρικό ρεύμα είναι ακόμα σε πρώιμο στάδιο, και έχει αρκετά υψηλό κόστος, αλλά βελτιώνεται με ιδιαίτερα ταχείς ρυθμούς. Τα κελία καυσίμου στο παρελθόν αποτελούσαν λύσεις για παραγωγή ηλεκτρικής ενέργειας, σε πολύ εξειδικευμένες κατασκευές όπως είναι οι διαστημοσυσκευές. Στις προηγούμενες δεκαετίες η τεχνολογία των κελιών καυσίμου ήταν οικονομικά ασύμφορη και όχι και τόσο αποδοτική. Γίνεται ανάλυση των επιμέρους δυσκολιών για την βελτιστοποίηση των συστημάτων τεχνολογίας κελιών καυσίμου και οι τρόποι επίλυσης τους που έχουν προταθεί. Το θεωρητικό μέρος της διπλωματικής συμπληρώνεται από την πειραματική μελέτη, που πραγματοποιήθηκε σε μία εμπορική εφαρμογή. Επίσης, με την βοήθεια ηλεκτρονικού υπολογιστή έγιναν προσομοιώσεις όλων των θεωρητικών μοντέλων που έχουν προταθεί από διάφορους επιστήμονες, πρωτοπόρους στην τεχνολογία των κελιών καυσίμου. Η εμπορική εφαρμογή που χρησιμοποιήθηκε για την εξακρίβωση των θεωρητικών παρατηρήσεων, καλύπτει μόνο ένα μέρος της τεχνολογίας των κελιών καυσίμου, καθώς ήταν μια στοίβα κελιών καυσίμου τεχνολογίας PEM. Τα κελιά καυσίμου τεχνολογίας PEM είναι τα πιο απλά στην κατασκευή και την χρήση, και είναι μια εφαρμοσμένη τεχνολογία εδώ και δεκαετίες. Οι υπόλοιπες τεχνολογίες απαιτούν διαφορετικές συνθήκες λειτουργίας και πολλές από αυτές βρίσκονται σε πειραματικό στάδιο. Τα κελία καυσίμου υψηλών θερμοκρασιών είναι ένα σημαντικό τεχνολογικό επίτευγμα που υπόσχεται πολλά. Η παρούσα διπλωματική αποτελεί ένα πολύ χρήσιμο εργαλείο για την κατανόηση της λειτουργίας ενός κελιού καυσίμου, καθώς και την κατανόηση των διαφόρων θερμοδυναμικών και ηλεκτροχημικών φαινομένων τα οποία συμβαίνουν μέσα στο κελί καυσίμου και είναι υπεύθυνα για την παραγωγή της ηλεκτρικής ενέργειας. Εκθέτονται όλοι οι λόγοι που οδηγούν στην ανάγκη μοντελοποίησης της λειτουργίας των κελιών καυσίμου. Παρουσιάζονται όλα τα μοντέλα τα οποία έχουν προταθεί κατά καιρούς και βοηθούν στην βαθύτερη κατανόηση της λειτουργίας ενός κελιού καυσίμου. 4 Επίσης, γίνεται σύγκριση των υπαρχόντων μοντέλων με την βοήθεια πειραματικής διάταξης, όπου συγκρίνονται τα πειραματικά αποτελέσματα με τα θεωρητικά. Το καύσιμο του μέλλοντος είναι το υδρογόνο και αυτό δύσκολα μπορεί κανείς να το αμφισβητήσει. Υπάρχουν εδώ και μια δεκαετία εφαρμοσμένες λύσεις σε αυτόνομα και διασυνδεδεμένα συστήματα, τα οποία λειτουργούν εξ’ ολοκλήρου με κελιά καυσίμου. Η μελλοντική ανάπτυξη τέτοιων συστημάτων αναμένεται μεγάλη δεδομένου των ενεργειακών προβλημάτων που αντιμετωπίζει η παγκόσμια κοινότητα σήμερα. Πρόκειται για συστήματα τα οποία μπορούν να δώσουν ανεξαρτησία και φιλική προς το περιβάλλον ενέργεια. Οι εναλλακτικές μορφές ενέργειας αποτελούν σημαντική λύση στη δραματική μείωση των ορυκτών πόρων και πρέπει η έρευνα και η αγορά να στραφούν προς την εκμετάλλευσή τους. / This Essay presents all the theoretical and technical attributes of the Fuel Cell technology. There is a thorough analysis of the available fuel cell technologies and also a historic review. Fuel cells, and specially Hydrogen as fuel, will play a significant role during the next decades. This technology develops at an escalated rate. Fuel Cells have a wide range of applications, due to their environmental friendly operation. The working principal of fuel cells is known for many years, the problem is the efficiency improvement of these systems. The transformation of Hydrogen to electricity has a significant cost today, but is estimated to be decreased as the rate of fuel cell usage is increased. Global warming due to carbon dioxide emissions lead to the need of a more efficient and clean fuel. The high rate of development of Hydrogen fuel cell technology means that fuel cell systems will have many more applications than they had in the past. Fuel cell technology was only applied as a power source for very special applications such as space shuttles and generally space devices. The main difficulties for fuel cell operation optimization are discussed here, so as the ways to solve these problems. The theoretical part of this essay is completed with the experimental study made on a commercial application. Moreover, with computer aided simulations, all the theoretical data was compared with the experimental. Theoretical electrical models that had been proposed by many scientists are presented and the results were also compared to the experimental data. This comparison covers only a certain part of the fuel cell technology, that of low temperature proton exchange membrane fuel cells. PEM fuel cells are much easier to construct and operate. This technology is well known for many years, as it has been applied by NASA for over 50 years. The rest of fuel cell types require special working conditions and many of them are in an experimental stage. For example, the much promising technology of high temperature PEM fuel cells. This essay is of great importance for scientist to understand the working principals of fuel cells and the various thermodynamic and electrochemical phenomena taking place inside the fuel cell. These phenomena are responsible for the production of the electrical energy. The need for theoretical modelling of fuel cells is also discussed and analysed. A review of the proposed pem fuel cell models is also made. The fuel of the future is definitely hydrogen and that’s a fact not easily questioned. The future development of hydrogen fuel cell systems for autonomous and interconnected electric power production is expected very high. These systems can produce clean and environmentally friendly energy. Renewable power sources are the most important solution to the global warming problem.

Made available in DSpace on 2014-10-09T12:27:00Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:30Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:27:00Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:30Z (GMT). No. of bitstreams: 0 / Neste trabalho foram selecionadas, estabelecidas e estimadas possíveis fontes de produção de hidrogênio para a geração de energia elétrica de forma distribuída, com a utilização de célula a combustível. Estudaram-se três fontes de geração de energia renovável no Brasil: a biomassa, a energia solar fotovoltaica e a energia eólica. Para o estabelecimento dos valores numéricos foram avaliadas as principais culturas agrícolas de cada estado pertencente à respectiva região e a quantidade de biomassa, na forma de rejeito agrícola, capaz de ser gerada para futura utilização na produção de hidrogênio. Da mesma maneira foi investigada e avaliada numericamente a capacidade de produção de hidrogênio através das energias eólica e solar fotovoltaica para cada região do Brasil, tomando-se como base o processo de eletrólise. Mediante os resultados obtidos é possível demonstrar as potencialidades do Brasil para a geração de energia elétrica de maneira distribuída e com a substituição de combustíveis fósseis e por conseqüência, com a melhoria do meio ambiente. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Multi-component coatings and high entropy alloys have in recent years attracted great interest for research, since they have shown to exhibit properties greater than the com- ponents of their parts. Today’s climate challenges requires transitioning from fossil fuels to renewable energy sources which demands use of new technology and new innovations. The hydrogen fuel cell is a technology which produces no carbon emissions, and the drive for innovation has led researchers to apply multi-component (high entropy alloys) coatings to invent the next generation hydrogen fuel cells and help the transition to renewable energy sources. This thesis has investigated the process-structure-property relationships of four deposi- tion growth parameters: target current (Itarget), argon pressure (PAr). substrate bias (Vsubstrate) and deposition time (tdeposition) on TiNbZrTa-coatings, grown by magnetron sputtering using an industrial deposition system. The range of the parameters have been: Itarget from 2.5 to 6 A, PAr from 1 to 17 mTorr, Vsubstrate from 30 to 200 V and tdeposition from 3.6 to 12 minutes (depending on Itarget). Coatings have been grown on Si (001) and stainless steel 304 and 316L substrates. The coating microstructure was analyzed by X-ray diffraction and electron microscopy. The results have yielded that all coatings are equimolar and that the coatings exhibit three different morphologies, two different topologies and two different corresponding structures. The different morphologies are wave, coarse columnar and fine columnar morphology. The two topologies are nodular and dune surface topology. The two different structures are a solid solution BCC (110) phase and an amorphous or nanocrystalline phase. The results indicate that parameters affecting the temperature of the substrate (Tsubstrate) is the prime decider for the final morphology of the coatings. High Itarget and Vsubstrate, low PAr and long tdeposition all increases Tsubstrate and results in a coating which exhibits a fine columnar morphology, dune topology and a solid solution BCC phase. These types of coatings have also proven to have improved corrosion resistance compared to the other type of coatings seen in this thesis. The other kind of coating is grown with low Itarget and Vsubstrate, high PAr and short tdeposition, which causes minimal increase of Tsubstrate. These growth parameters result in a coating with coarse columnar morphology, nodular topology and amorphous or nanocrystalline phase, with less corrosion resistance. / FunMat II

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.

[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