The global hydrogen demand is steadily increasing, and one way of accelerating the green hydrogen supply is to stimulate the green hydrogen economy. Utilization of waste heat from hydrogen production can increase the profitability of produced green hydrogen. Therefore, the aim of this study is to propose a system for integration of waste heat on the district heating (DH) network in Luleå, Sweden. Furthermore, an economic evaluation of the proposed system was conducted. In this study, the system was developed and investigated for two cases i.e. for a PEM and alkaline electrolyzer with an installed capacity of 100 MW. A large-scale heat pump and a heat exchanger were further added to the system to integrate the waste heat on the DH-network, while simultaneously providing cooling to the electrolyzer stack. The system was modelled for static conditions in the software MATLAB, with retrieved hourly DH data from Luleå Energi. The results showed that 203 060 MWhth can be extracted from the PEM electrolyzer with a waste heat temperature of 79 oC, while 171 770 MWhth can be integrated on the DH network annually. For the alkaline electrolyzer, 310 630 MWhth can be extracted at a waste heat temperature of 80 oC, while 226 220 MWhth can be integrated on the DH annually. The overall system efficiency is 94.7 % and 88.4 % for PEM and alkaline connected systems, respectively. Furthermore, the Levelized Cost of Heat (LCOH) is 0.218 SEK/kWhth and 0.23 SEK/kWhth for a PEM and alkaline connected system, respectively. For future scenarios with fourth generation of DH-networks, it is predicted that the LCOH can reach 0.018 SEK/kWth for a PEM electrolyzer system, and 0.017 SEK/kWth for an alkaline electrolyzer system. One conclusion that can be drawn from this study is that the utilized heat from the proposed system is price competitive in comparison with other thermal energy sources.

The objective of the current research is to study the effect of mechanical vibration on catalyst layer degradation via Platinum (Pt) particle agglomeration and growth in the membrane electrode assembly (MEA) of a proton exchange membrane fuel cell (PEM Fuel Cell). This study is of great importance, since many PEM fuel cells operate under a vibrating environment, such as the case of vehicular applications, and this may influence the catalyst layer degradation and fuel cell performance. Through extensive literature review, there are only few researches that have been studied the effect of mechanical vibration on PEM fuel cells. These studies focused only on PEM fuel cell performance under vibration for less than 50 hours and none of them considered the degradation of the fuel cell components, such as MEA and its catalyst layer. To study the effect of the mechanical vibration on the catalyst layer an accelerated test with potential cycling was specially designed to simulate a typical vehicle driving condition. The length of the accelerated test was designed to be 300 hour with potential cycling comprised of idle running, constant load, triangle (variable) load and overload running at various mechanical vibration conditions. These mechanical vibration conditions were as follows: 1g 20 Hz, 1g 40 Hz, 4g 20 Hz and 4g 40 Hz. No vibration tests were also conducted to study the influence of operating time and were used as a baseline for comparison study. The series of accelerated tests were followed by microscopy and spectroscopy analyses using environmental scanning electron microscopy (ESEM), transmission electron microscopy (TEM) and X-Ray diffraction (XRD). An ESEM was used to qualitatively analyze pristine and degraded catalyst. TEM and XRD were used to quantitatively analyze catalyst layer degradation via Pt agglomeration and growth in pristine and degraded states. For each test condition, PEM fuel cell performance by means of Voltage - Current (VI) curves was monitored and recorded. It was observed that the mean diameter of Pt particles tested under mechanical vibration is 10% smaller than the ones that were tested under no vibration conditions. The Pt particles in the order of 2 to 2.5 nm in the pristine state have grown to 6.14 nm (after 300 hour accelerated test at no vibration condition), to 5.64 nm (after 300 hours accelerated test under 4g 20 Hz vibration condition) and to 5.55 nm (after 300 hours accelerated test under 1g 20 Hz vibration condition). The mean Pt particle diameters, after 300 hour accelerated test under 1g 40 Hz and 4g 40 Hz vibration conditions, were 5.89 nm. With an increase of the mean Pt particle diameter, the active surface area of the catalyst layer of the MEA decreases and as a result, performance of MEA and PEM fuel also decreases. It was observed that performance of the MEA tested under no vibration condition is about 10% lower than the one tested under 1g 20 Hz. The VI curve showed that the lowest performance of the MEA after 300 hour accelerated test corresponded to no vibration conditions and equaled to 7.85 Watts at 0.5 V (Pt particle size ~ 6.14 nm) and highest performance, corresponded to the MEA tested under 1g 20 Hz, and equaled to 8.66 Watts at 0.5 V (Pt particle size ~ 5.55 nm). / Mechanical Engineering

La presente Tesis Doctoral titulada "Estudio del comportamiento estacionario y dinámico de una pila de combustible de 300 W de potencia operando en modos ánodo cerrado y ánodo abierto" se estudia el efecto de las variables de operación de la pila de combustible como son los caudales de hidrógeno y de aire, la temperatura de operación, la temperatura de humidificación de los gases, los coeficientes estequiométricos de los gases y la presión de alimentación de los mismos sobre el comportamiento de una pila de combustible de 300W y de las celdas individuales que la componen, mediante las curvas potencial-densidad de corriente o curvas de polarización y mediante espectroscopía de impedancias electroquímicas. Para llevar a cabo el trabajo se ha desarrollado un sistema de monitorización y control de las variables mencionadas previamente. Las curvas de polarización son características de cada pila de combustible, y permiten estudiar su comportamiento estacionario en diferentes condiciones de operación. En modo ánodo cerrado el potencial aumenta con el coeficiente estequiométrico del aire. En modo ánodo abierto, el potencial aumenta con los coeficientes estequiométricos del hidrógeno y del aire, con los caudales de ambos gases y con la presión. Con respecto a la temperatura, en ambos modos de operación, los mejores resultados se obtienen cuando la temperatura de operación y de humidificación tienen valores similares. Se ha desarrollado un modelo matemático que permite determinar los parámetros cinéticos de las celdas individuales mediante el ajuste de las curvas de polarización experimentales al modelo propuesto. Al estudiar el comportamiento dinámico se ha observado que cuando se produce un aumento de la densidad de corriente el potencial disminuye bruscamente, alcanza un valor mínimo o subimpulso y luego aumenta hasta alcanzar un nuevo estado estacionario. Por otro lado, cuando se produce un cambio negativo en la densidad de corriente el potencial aumenta hasta un valo / Pérez Page, M. (2012). ESTUDIO DEL COMPORTAMIENTO ESTACIONARIO Y DINÁMICO DE UNA PILA DE COMBUSTIBLE TIPO PEM DE 300 W OPERANDO EN LOS MODOS DE OPERACIÓN DE ÁNODO CERRADO O DEAD-END Y ÁNODO ABIERTO [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/16960

Cette thèse s'inscrit dans le contexte de la production et de l'utilisation du vecteur énergétique hydrogène dont le potentiel est très prometteur dans un paysage énergétique renouvelé. Plus exactement, cette étude traite des électrolyseurs et des piles à combustible de technologie PEM (membranes échanges de protons) fonctionnant à basse température. Dans une très large majorité, les études présentées ici se sont inscrites en partenariat étroit avec HELION Hydrogen Power, notamment dans le cadre du projet ANR AIRELLES (2008- 2011). Tout d'abord sont posées les bases de modèles (quasi-statique, dynamique petits signaux, dynamique forts signaux) génériques et applicables à une pile à combustible et à un électrolyseur. Les méthodologies de caractérisation ainsi que les techniques de paramétrisation de ces modèles utilisées sont ensuite exposées. L'intérêt de croiser toutes ces approches pour caractériser au plus juste les composants est illustré. A partir de cette vision commune des deux composants, le document est scindé en trois parties : - Une première partie porte sur une validation et une exploitation des modèles proposés via différentes études sur des piles à combustible alimentées en H2/air : 1) La recherche de signatures d'un engorgement et d'un assèchement d'une pile alimentée en H2/air. Ces signatures sont comparées à celles d'une pile alimentée en H2/02. 2) L'analyse des impacts d'harmoniques de courant hautes fréquences (représentatives d'un convertisseur continu-continu de type boost) sur un coeur de pile. Ces travaux s'inscrivent dans le cadre d'une collaboration avec le laboratoire FEMTO-ST/FCLAB (projet CNRS CO-CONPAC). - Une seconde partie porte sur la validation et la paramétrisation des modèles proposés pour l'électrolyseur. Deux techniques originales ont été proposées et testées : la première consiste en une approche multispectres d'impédance et la seconde en une approche multibalayages basses fréquences. - Une troisième partie décrit les moyens d'essais qui ont été conçus et déployés au cours de cette thèse aboutissant à une plateforme significative de tests dédiée à l'hydrogène sur le site l'INPT (Toulouse Labège). / This thesis is part of the production and use of hydrogen energy vector whose potential is very promising in a renewable energy landscape. More precisely, this study focuses on electrolysers and fuel cell using PEM technology (proton exchange membrane) operating at low temperature. Almost all the studies presented here were executed in close partnership with HELION Hydrogen Power; particularly in the context of the ANR project "AIRELLES" (2008-2011). Firstly are presented bases for models (steady-state, small signal dynamics, large signal dynamics) that are generic and applicable to a fuel cell and an electrolyzer. The characterization methodologies and parameterization techniques used are then presented. The interest to interbreed all these approaches to exactly characterize the components is illustrated. Using this common view of the two components, the document is divided into three parts: - The first part focuses on validation and exploitation of the proposed models through various studies on H2/air fuel cells: 1) The search for signatures of a flooding or a drying stack fuelled in H2/air. These signatures are compared with stack fuelled in H2/02. 2) The analysis of the impacts of high frequency current harmonics (representative of a DC-DC boost converter) on a cell heart. This work is part of collaboration with the laboratory FEMTO-ST/FCLAB (CNRS project CO-CONPAC). - A second part focuses on the validation and parameterization of models proposed for the electrolyzer. Two new techniques have been proposed and tested: the first one is a multispectral impedance approach and the second one a low frequencies multi sweep approach. - The third part describes the test facilities that have been designed and implemented in this thesis leading to a significant test platform dedicated to hydrogen on INPT site (Toulouse Labège).

Un coeur de pile à combustible est un système multi-physique couplant des phénomènes de transport de matière et de charges (dans les électrodes et l'électrolyte), et de cinétique électrochimique (au niveau des sites réactionnels) ; phénomènes auxquels s'ajoutent des problèmes de thermique et de distribution des gaz réactifs. De nombreux modèles permettent de décrire localement ces phénomènes, par le biais d'équations aux dérivées partielles faisant intervenir l'espace et le temps. Ces modèles, aussi précis soient-ils, ne sont en pratique guère utilisables dans une approche système, dès lors que l'on cherche à étudier un ensemble complexe dans lequel le coeur de pile n'est qu'un élément parmi d'autres. Il existe bien des modèles dynamiques semi-empiriques pour lesquels la cellule électrochimique est représentée par un circuit électrique équivalent dont certains paramètres sont déterminés expérimentalement, par des mesures spectroscopiques en particulier. L'inconvénient de cette approche vient de ce que les modèles obtenus, de type "petits signaux", ne sont en toute rigueur valables qu'autour d'un point de fonctionnement. Les travaux présentés dans ce mémoire traite du développement, de la validation expérimentale et de l'exploitation d'un modèle électrique local 1D de cellule de pile à combustible PEM, de type circuit pour une implantation directe dans les logiciels de simulation des systèmes électriques (Saber® dans notre cas), et dont les éléments sont calculés par analogie électrique à partir des phénomènes physiques dont la pile est le siège. Ce modèle est dynamique, il rend compte du phénomène de couche double électrique, et de l'influence des conditions opératoires, notamment l'alimentation en gaz (sur-alimentation, sous-alimentation transitoire), sur le comportement électrique et les performances de la cellule. Le premier chapitre fait un état des lieux des modèles de pile existants, et permet de situer notre travail dans ce contexte. Le chapitre 2 est consacré à la mise en équation traduisant les phénomènes : transport des gaz dans les couches de diffusion et de l'eau dans la membrane, transport des charges dans les électrodes et la membrane, cinétique électrochimique aux interfaces membrane-électrode, couche double électrique, conditions aux limites. Nous y détaillons également la représentation analogique permettant de traiter les équations de transport dans un environnement de calcul dédié à la simulation des systèmes électriques, ainsi que le modèle électrique complet. Une comparaison avec un modèle similaire implanté dans un logiciel utilisant la méthode des éléments finis, est proposée, de même qu'une validation expérimentale, en régime stationnaire et en régime transitoire. Le dernier chapitre traite de l'exploitation du modèle à des fins d'étude paramétrique (conditions opératoires, paramètres physiques), et de simulation "systèmes" (fonctionnements particuliers, mise en série, association avec un convertisseur) / A heart of a fuel cell is a multi-physics system that couples mass and charge transport phenomena (in electrodes and electrolyte), and electrochemical kinetics at reactive sites ; to these phenomena, are added thermal transfer, and gas distribution problems. Many mathematical models have already been developed in order to describe locally these phenomena, through partial differential equations involving space and time. Theses models are often accurate, but they are hardly used in a system approach, since one aims to study a complex system in which the fuel cell is only one element among others. Many semi-empirical dynamics models have also been developed, with an electrochemical cell represented by an equivalent electrical circuit, the parameters of which are often determined experimentally, by spectroscopy measurements in particular. The main drawback of this approach is that it results in small signal models, which are theoretically only available around an operating point. The works presented in this thesis deals with the development, the experimental validation and the use of a 1D local PEM fuel cell model, of circuit type for a direct implementation in simulation software commonly used in electrical engineering (Saber® in our case). The elements of the model are determined by using electrical analogy of physical phenomena that occur in the fuel cell. The model is dynamic, and takes into account electric double layer, and influence of operating conditions (notably gas supply effects, such as over-feeding or transient gas starvation) on fuel cell performances. The first chapter presents literature review on existing fuel cell models, and enable to situate our work in this context. We give in chapter 2 local equations on which our model is based: gas transport in diffusion layers, water transport in the membrane, charge transport in electrodes and membrane, electrochemical kinetics at the membrane-electrode interfaces, electric double layer, boundary conditions. Then we detail the analogy representation that allows to compute transport equations by means of electrical engineering simulation software, as well as to complete electrical model. A comparison with a similar model implemented in a software using the finite element method is proposed, then an experimental validation in steady and transient state is carried out. The last chapter deals with the exploitation of the model for parametric study purposes (operating conditions, physical parameters), and for system simulation purposes (specific operations of a single cell, multi-cells in series, association with a power electronic converter)

Les systèmes piles à combustible de type PEM pour des applications de transport reposent sur un ensemble d’auxiliaires (stockage d’hydrogène, compresseur d’air, convertisseur de puissance, humidificateur, etc) qui assurent le bon fonctionnement du système pile. La mise en place d’observateurs permet de disposer d’un outil pour reconstruire les états non mesurés de ce système; cela permet de mettre en place un contrôle par retour de sortie en vue d’optimiser les performances du système pile et ainsi d'améliorer la détection et l’isolation de défauts (FDI). Cette thèse est basée sur l’étude et la synthèse d'observateurs adaptatifs par mode glissant d’ordre supérieur, pour deux principaux auxiliaires de la pile que sont, le système d'alimentation en air et les convertisseurs de puissance associés à la pile. La première partie de la thèse est consacrée à la synthèse d’observateurs pour la reconstruction des états et à la détection et l’isolation des défauts sur le système d’alimentation en air de la PEMFC. Dans un premier temps, un observateur algébrique par mode glissant d’ordre supérieur est synthétisé pour la reconstruction de la pression partielle de l'oxygène et de l'azote. Dans un deuxième temps, un nouvel observateur adaptatif par mode glissant d’ordre deux est synthétisé pour assurer l'observation simultanée des états, l'identification des paramètres, la surveillance et la reconstruction de défaut dans le circuit d’air. Les performances des observateurs proposées ont été validées grâce à un simulateur Hardware-In-Loop (HIL) du système pile à combustible.Dans la deuxième partie, nous nous sommes intéressés à l’élaboration d’observateurs et de commande par retour de sortie pour les convertisseurs associé au système pile dans une application transport. Ainsi, une commande novatrice par mode glissant d’ordre deux, de type retour de sortie, a été élaborée pour le convertisseur AC/DC. Dans un second temps, un observateur de type modes glissants d’ordre 2 adaptatif est synthétisé pour un convertisseur de type multicellulaire. / Automotive PEM Fuel Cell systems rely upon a set of auxiliary systems for proper operation, such as humidifier, air-feed compressor, power converter etc. The internal physical states of the latter are often unmeasurable, yet required for their precise control. Observers provide a means of obtaining the unmeasured states of these auxiliary systems for feedback control, optimal energy consumption and Fault Diagnosis and Isolation (FDI). This thesis is based on higher order sliding mode observer design studies for two major PEMFC auxiliary systems found in modern automobiles, the air-feed system and the power electronics system.The first part is focused on robust observation and FDI of the PEMFC air-feed systems. Sliding mode observer design and their applications to FDI have been studied in detail for this purpose and the key observation problems in this system have been identified. Based on this study, two solutions are proposed, a sliding mode algebraic observer for oxygen and nitrogen partial pressures and a novel robust adaptive-gain Second Order Sliding Mode (SOSM) observer based FDI for simultaneous state observation, parameter identification, health monitoring and fault reconstruction of the PEMFC air-feed system. The performance of the proposed observers has been validated on an instrumented Hardware-In-Loop (HIL) test bench.The observation and output feedback control problems of different power electronic converters, commonly found in fuel cell vehicles, are addressed in the next part. Robust output feedback SOSM control for three phase AC/DC converters have been presented. A robust SOSM observer for multi-cell converters has also been designed. The performance of all these designs has been demonstrated through a multi-rate simulation approach. The results highlight the robustness of the observers and controllers against parametric uncertainty, measurement noise and external disturbance.

Hydrogen fuel cells are devices used to generate electricity from the electrochemical reaction between air and hydrogen gas. An attractive advantage of these devices is that their byproduct is water, which is very safe to the environment. However, hydrogen fuel cells still lack some improvements in terms of increasing their life time and electricity production, decreasing power losses, and optimizing their operating conditions. In this thesis, the cathode part of the hydrogen fuel cell will be considered. This part mainly consists of an air gas channel and a gas diffusion layer. To simulate the fluid dynamics taking place in the cathode, we present two models, a general model and a simple model both based on a set of conservation laws governing the fluid dynamics and chemical reactions. A numerical method to solve these models is presented and verified in terms of accuracy. We also show that both models give similar results and validate the simple model by recovering a polarization curve obtained experimentally. Next, a shape optimization problem is introduced to find an optimal design of the air gas channel. This problem is defined from the simple model and a cost functional, $E$, that measures efficiency factors. The objective of this functional is to maximize the electricity production, uniformize the reaction rate in the catalytic layer and minimize the pressure drop in the gas channel. The impact of the gas channel shape optimization is investigated with a series of test cases in long and short fuel cell geometries. In most instances, the optimal design improves efficiency in on- and off-design operating conditions by shifting the polarization curve vertically and to the right. The second primary goal of the thesis is to analyze mathematical issues related to the introduced shape optimization problem. This involves existence and uniqueness of the solution for the presented model and differentiability of the state variables with respect to the domain of the air channel. The optimization problem is solved using the gradient method, and hence the gradient of $E$ must be found. The gradient of $E$ is obtained by introducing an adjoint system of equations, which is coupled with the state problem, namely the simple model of the fuel cell. The existence and uniqueness of the solution for the adjoint system is shown, and the shape differentiability of the cost functional $E$ is proved.

Hydrogen fuel cells are devices used to generate electricity from the electrochemical reaction between air and hydrogen gas. An attractive advantage of these devices is that their byproduct is water, which is very safe to the environment. However, hydrogen fuel cells still lack some improvements in terms of increasing their life time and electricity production, decreasing power losses, and optimizing their operating conditions. In this thesis, the cathode part of the hydrogen fuel cell will be considered. This part mainly consists of an air gas channel and a gas diffusion layer. To simulate the fluid dynamics taking place in the cathode, we present two models, a general model and a simple model both based on a set of conservation laws governing the fluid dynamics and chemical reactions. A numerical method to solve these models is presented and verified in terms of accuracy. We also show that both models give similar results and validate the simple model by recovering a polarization curve obtained experimentally. Next, a shape optimization problem is introduced to find an optimal design of the air gas channel. This problem is defined from the simple model and a cost functional, $E$, that measures efficiency factors. The objective of this functional is to maximize the electricity production, uniformize the reaction rate in the catalytic layer and minimize the pressure drop in the gas channel. The impact of the gas channel shape optimization is investigated with a series of test cases in long and short fuel cell geometries. In most instances, the optimal design improves efficiency in on- and off-design operating conditions by shifting the polarization curve vertically and to the right. The second primary goal of the thesis is to analyze mathematical issues related to the introduced shape optimization problem. This involves existence and uniqueness of the solution for the presented model and differentiability of the state variables with respect to the domain of the air channel. The optimization problem is solved using the gradient method, and hence the gradient of $E$ must be found. The gradient of $E$ is obtained by introducing an adjoint system of equations, which is coupled with the state problem, namely the simple model of the fuel cell. The existence and uniqueness of the solution for the adjoint system is shown, and the shape differentiability of the cost functional $E$ is proved.

A l'aide de la Représentation Energétique Macroscopique (REM) comme outil de modélisation graphique, la modélisation et la gestion d'énergie d'une application stationnaire isolée à base d'un système PEMFC couplé à l'énergie solaire photovoltaïque comme source principale d'énergie sont développées. Afin d'assurer une autonomie du système en combustible, un électrolyseur PEM est intégré au dispositif. En outre, des packs de batteries et de supercondensateurs permettent un stockage d'énergie et de puissance.Grâce à la modularité de la REM, les modèles respectifs des différentes entités énergétiques du système ont été développés avant de les assembler pour reconstituer un modèle global. Une caractéristique propre de la REM étant la commande, une Structure Maximale de Commande (SMC) est déduite du modèle REM du système par application de règles d'inversion.Le phénomène d'effet échelle a permis de dimensionner le système grâce à un profil de consommation domestique d'énergie électrique. Une stratégie de gestion énergétique basée sur la méthode du bilan des flux de puissance et prenant en compte les dynamiques de chaque source a été développée. Différents modes de fonctionnement ont été étudiés. Grâce è un profil d'ensoleillement d'une journée, la pertinence du modèle a été évaluée. Il a été en outre introduit un couplage entre la méthode du bilan des flux de puissance et la logique floue afin que la stratégie de gestion redéfinisse les références des grandeurs électriques en tenant compte de l'état de charge des batteries et de celui des supercondensateurs.

Hydrogen fuel cells are devices used to generate electricity from the electrochemical reaction between air and hydrogen gas. An attractive advantage of these devices is that their byproduct is water, which is very safe to the environment. However, hydrogen fuel cells still lack some improvements in terms of increasing their life time and electricity production, decreasing power losses, and optimizing their operating conditions. In this thesis, the cathode part of the hydrogen fuel cell will be considered. This part mainly consists of an air gas channel and a gas diffusion layer. To simulate the fluid dynamics taking place in the cathode, we present two models, a general model and a simple model both based on a set of conservation laws governing the fluid dynamics and chemical reactions. A numerical method to solve these models is presented and verified in terms of accuracy. We also show that both models give similar results and validate the simple model by recovering a polarization curve obtained experimentally. Next, a shape optimization problem is introduced to find an optimal design of the air gas channel. This problem is defined from the simple model and a cost functional, $E$, that measures efficiency factors. The objective of this functional is to maximize the electricity production, uniformize the reaction rate in the catalytic layer and minimize the pressure drop in the gas channel. The impact of the gas channel shape optimization is investigated with a series of test cases in long and short fuel cell geometries. In most instances, the optimal design improves efficiency in on- and off-design operating conditions by shifting the polarization curve vertically and to the right. The second primary goal of the thesis is to analyze mathematical issues related to the introduced shape optimization problem. This involves existence and uniqueness of the solution for the presented model and differentiability of the state variables with respect to the domain of the air channel. The optimization problem is solved using the gradient method, and hence the gradient of $E$ must be found. The gradient of $E$ is obtained by introducing an adjoint system of equations, which is coupled with the state problem, namely the simple model of the fuel cell. The existence and uniqueness of the solution for the adjoint system is shown, and the shape differentiability of the cost functional $E$ is proved.