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Study of Dehydrogenation Properties of Metallic Borohydrides for Hydrogen Storage Parviz Hajiyev

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Study of Dehydrogenation Properties of Metallic Borohydrides for Hydrogen Storage Parviz Hajiyev Study of dehydrogenation properties of metallic borohydrides for hydrogen storage Parviz Hajiyev To cite this version: Parviz Hajiyev. Study of dehydrogenation properties of metallic borohydrides for hydrogen storage. Materials Science [cond-mat.mtrl-sci]. Université Grenoble Alpes [2020-..], 2020. English. NNT : 2020GRALY003. tel-02939130 HAL Id: tel-02939130 https://tel.archives-ouvertes.fr/tel-02939130 Submitted on 15 Sep 2020 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. THÈSE Pour obtenir le grade de DOCTEUR DE L'UNIVERSITE GRENOBLE ALPES Spécialité : Physique des Matériaux Arrêté ministériel : 25 mai 2016 Présentée par « Parviz HAJIYEV » Thèse dirigée par François RIEUTORD, Directeur de Recherche, Institut de recherche interdisciplinaire de Grenoble (IRIG-CEA), et codirigée par Vasile IOSUB, Ingénieur de Recherche, Laboratoire d'Innovation pour les Technologies des Energies Nouvelles (LITEN - CEA) préparée au sein du Laboratoire d'Innovation pour les Technologies des Energies Nouvelles (LITEN - CEA) dans l'Ecole Doctorale de Physique - GRENOBLE Etude des propriétés de déshydrogénation des borohydrures métalliques pour le stockage de l’hydrogène Thèse soutenue publiquement le « 22 Janvier 2020 », devant le jury composé de : M. Olivier ISNARD Professeur, Directeur de l’Ecole Doctorale de Physique de Grenoble, Président M. Yaroslav FILINCHUK Professeur, Institute of Condensed Matter and Nanosciences (IMCN) Université Catholique de Louvain (UCL), Rapporteur M. Umit DEMIRCI Professeur, Département de Chimie de l’Université de Montpellier, Rapporteur M. Michel LATROCHE Directeur de Recherche, l’Institut de Chimie et des Matériaux Paris-Est (CNRS), Membre M. Michel BARDET Directeur de Recherche, Institut de recherche interdisciplinaire de Grenoble (IRIG-CEA), Membre 1 “You are not a drop in the ocean, you are the entire ocean in a drop” Mevlana Rumi “Science without religion is lame, religion without science is blind.” Albert Einstein “Any sufficiently advanced technology is indistinguishable from magic.” Arthur C. Clarke I dedicate this thesis work to my family who supported me unconditionally in every step of my life. Bu tezis işini həyatımın hər addımında məni sonuna qədər şərtsiz bir şəkildə dəstəkləyən ailəmə həsr edirəm. 2 Acknowledgements This thesis project was a test of my physiological endurance more than my technical competences and knowledge of science. Maybe that is what a PhD supposed to be. I didn’t have that romanticized mentor-student relationship during my thesis but I didn’t succeed in this endeavor solely on my own. Sometimes the best help one can give you is a boost of motivation. My supervisors almost at every opportunity expressed their confidence in my ability to carry the task. According to my peers, most PhD students are not as lucky. So in hindsight, the persistent positive encouragement of my supervisors was the key to my success. I’d like to thank to my thesis director Francois Rieutord for enabling the smooth continuation of my activities however he can, guiding me to the right expert and the equipment whenever my research activities arrived at an impasse. I am grateful to Michel Bardet for his always friendly and accommodating approach to my problems, for teaching me how to use solid state NMR which without it the quality of my scientific arguments and the success of this thesis work would have been questionable. I shared the same office for three years with my supervisor Vasile Iosub, a luxury most PhD students don’t have. I thank him for tolerating my spontaneous interruptions regardless whether the topic of the question was scientific, personal or anything in between. I express my gratitude for his patience and willingness to solve my problems. I think number one priority of scientists is to preserve their child-like curiosity for topics and issues outside of their field of expertise. So I thank Vasile for not shying away from my lunch-time discussion topics, continuing to teach, listen and challenge my views in a very productive manner and more importantly I thank him for being a friend. I’d like to thank to Philippe Capron for giving me all the resources and the freedom to perform my research activities, for taking special interest in my progress and doing everything in his capacity to remove the barriers impeding my activities. Above everything else, during the times of uncertainty, I found his support and assurances were an important much-needed boost of motivation. I get to enjoy continuing my activities here in LITEN after my PhD. Many colleagues and friends expressed the rarity of this opportunity. So I am thankful to Philippe for giving me this valuable opportunity as well. Majority of my difficulties during my research activities in the lab were small, forgettable and not easily definable. I am very grateful for energetic and helpful support of my colleagues Isabelle Rougeaux and Jerome Delmas for swiftly overcoming most of these difficulties. I am convinced that a healthy psychology is the most important factor for a successful completion of a thesis work. This wouldn’t have been possible without my like-minded friends and most importantly without my girlfriend who constantly radiated with positive energy and made my life both inside and outside CEA a beautiful memory. 3 Acknowledgements ....................................................................................................................................... 3 Abstract ......................................................................................................................................................... 7 Résumé .......................................................................................................................................................... 9 Abbreviations .............................................................................................................................................. 11 I. State of the art.................................................................................................................................... 13 I.1. Introduction ............................................................................................................................... 13 I.2. Hydrogen economy ................................................................................................................... 13 I.2.1. Bigger Picture .................................................................................................................... 15 I.3. Physical hydrogen storage ........................................................................................................ 16 I.3.1. Compressed hydrogen ...................................................................................................... 16 I.3.2. Liquefied hydrogen ........................................................................................................... 16 I.3.3. Hydrogen in porous compound ........................................................................................ 17 I.4. Chemical hydrogen storage ...................................................................................................... 17 I.4.1. Hydrogen containing gases ............................................................................................... 18 I.4.2. Liquid organic hydrogen carriers .................................................................................... 19 I.4.3. Solid-state hydrogen storage ............................................................................................ 19 I.4.3.1. Metal hydrides ............................................................................................................... 19 I.4.3.2. Complex hydrides .......................................................................................................... 21 I.4.3.3. Metal amides .................................................................................................................. 21 I.4.3.4. Ammonia Borane ........................................................................................................... 21 I.4.3.5. Metal amidoboranes ...................................................................................................... 24 I.4.3.6. Metal borohydrides ....................................................................................................... 25 I.4.3.7. Metal borohydride derivatives ..................................................................................... 28 I.4.3.8. Composite Reactive hydrides ....................................................................................... 31 I.4.3.9. Hydrolysis ...................................................................................................................... 32 I.4.3.10. Direct hydrogenation catalysts ................................................................................ 33 I.4.3.11. Frustrated Lewis Pairs .............................................................................................. 34 I.5. Conclusion .................................................................................................................................
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