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Étude Du Polymère Élastomère À Base D'acrylonitrile, HNBR, Pour Son Application Dans Les Batteries Li-Ion

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Étude Du Polymère Élastomère À Base D'acrylonitrile, HNBR, Pour Son Application Dans Les Batteries Li-Ion Université de Montréal Étude du polymère élastomère à base d’acrylonitrile, HNBR, pour son application dans les batteries Li-ion par Nina Verdier Département de Chimie Faculté des arts et des sciences Thèse présentée à la Faculté des études supérieures et postdoctorales en vue de l’obtention du grade de Philosophiae doctor (Ph.D) en Chimie Novembre 2019 © Nina Verdier, 2019 Cette thèse intitulée : Étude du polymère élastomère à base d’acrylonitrile, HNBR, pour son application dans les batteries Li-ion Présentée par : Nina Verdier A été évaluée par un jury composé des personnes suivantes Karen Waldron Présidente du jury Dominic Rochefort Directeur de recherche Mickaël Dollé Co-directeur de recherche Richard Martel Membre du jury Joël Gaubicher Examinateur externe, Institut des Matériaux Jean Rouxel (Nantes) Ahmad Hamdan Représentant du doyen de la FAS Résumé Les travaux présentés portent sur l’étude du HNBR (Hydrogenated Nitrile Butadiene Rubber), un polymère à base d’acrylonitrile, pour son application en tant que liant d’électrodes dans les batteries lithium ions. Cette thèse repose sur un partenariat avec l’entreprise Hutchinson (spécialisée dans le domaine des polymères) qui a cherché à développer un nouveau procédé pour la fabrication des électrodes. Ce procédé par voie fondue a soulevé la problématique du polymère liant utilisé dans les électrodes puisque ce dernier doit être compatible avec le procédé tout en étant utilisable dans des batteries. C’est dans l’optique de trouver et valider un tel polymère que s’inscrit cette thèse sur le polymère HNBR. En premier lieu, nous nous sommes concentrés sur les répercussions du traitement thermique, étape importante du procédé par voie fondue, sur le HNBR. Il a été conclu que le traitement thermique conduit à une réticulation du polymère aidant ainsi à la stabilité chimique du HNBR dans les électrolytes organiques des batteries. Ensuite, le HNBR a été introduit comme liant d’électrodes et a été analysé, avec le procédé de fabrication classique puis avec le nouveau procédé. Nous avons remarqué que le HNBR est un bon candidat pour être utilisé dans un système électrochimique car il y est stable sur une large gamme de potentiels et permet d’obtenir des performances en cyclage et en puissance intéressantes. Face à ce constat, la dernière partie des travaux s’est concentrée sur une analyse approfondie du système en étudiant les interactions entre les fonctions polaires du HNBR, les nitriles, et les ions lithium présents dans l’électrolyte. La combinaison polymère-sel-solvant a été étudiée pour comprendre comment chacun de ces paramètres impacte les propriétés électrochimiques du système et en particulier la conductivité. Nous avons remarqué qu’un taux d’acrylonitrile élevé est favorable à une plus haute conductivité et que le solvant, de par son affinité avec le HNBR, est également à considérer. Mots-clés : Polymère, liant d’électrode, batterie lithium-ion, HNBR, élastomère, réticulation, nitriles. i Abstract In this thesis, we have investigated an acrylonitrile-based polymer, HNBR (Hydrogenated Nitrile Butadiene Rubber), for its application in lithium ion batteries. This work relies on a partnership with the company Hutchinson (specialized in polymers) who was interested in developing a new process for the fabrication of electrodes. This melt-based process revealed problems regarding the polymer that is used as a binder for the electrodes as it needs to be compatible with the process as well as with the application in batteries. The aim of the thesis was therefore to find and validate a polymer meeting these requirements. Hence, HNBR was investigated. At first, we focused on the thermal treatment of HNBR, a key step of the melt-process. It was concluded that the thermal treatment leads to the cross-linking of HNBR, which is an asset because it increases the chemical stability of HNBR in the presence of the organic electrolyte. The following step was to introduce HNBR into the electrode formulation and investigate the performances of electrodes, made with the classical process and then with the melt process. It was found that HNBR is a good candidate to be introduced in an electrochemical system because it is stable over wide potential ranges and it allows interesting cycling and power performance. Faced with these findings, the last part of the study was to focus on analyzing the system more deeply by investigating the interactions between the HNBR polar functions, nitriles, and the lithium ions from the electrolyte. The ternary system polymer-salt-solvent was analyzed to understand the impact of each of these parameters on electrochemical properties, especially the conductivity. We noticed a high acrylonitrile content was beneficial to have a higher conductivity and that the solvent, regarding its affinity with HNBR, needs also to be considered. Keywords: Polymer, binder for electrodes, Lithium-ion battery, HNBR, elastomer, crosslinking, nitriles. ii Table des matières Résumé ......................................................................................................................................... i Abstract ....................................................................................................................................... ii Table des matières...................................................................................................................... iii Liste des tableaux ..................................................................................................................... viii Liste des figures ......................................................................................................................... ix Liste des abréviations ............................................................................................................. xviii Remerciements ......................................................................................................................... xxi Chapitre 1 : Introduction générale .............................................................................................. 1 1.1 Dispositif de stockage d’énergie : les batteries ................................................................. 1 1.1.1 Généralités et contexte ............................................................................................... 1 1.1.2 Histoire des batteries .................................................................................................. 3 1.1.3 Fonctionnement des batteries ..................................................................................... 6 1.2 Composition des batteries Li-ion ...................................................................................... 8 1.2.1 L’électrolyte ............................................................................................................... 9 1.2.2 Les électrodes........................................................................................................... 10 1.2.3 Les matériaux actifs d’électrodes............................................................................. 11 1.2.3.a Électrode négative ............................................................................................. 12 1.2.3.b Électrode positive .............................................................................................. 14 1.3 Les liants existants dans les batteries Li-ion ................................................................... 15 1.3.1 Propriétés recherchées pour un polymère liant ........................................................ 16 1.3.2 Les types de polymères utilisés comme liant ........................................................... 16 1.3.2.a Les homopolymères .......................................................................................... 16 1.3.2.b Le mélange de polymères ................................................................................. 19 1.3.2.c Les copolymères................................................................................................ 21 1.4 Procédés de fabrication des électrodes pour batterie Li-ion ........................................... 22 1.4.1 Procédé par voie humide .......................................................................................... 22 1.4.2 Procédés sans solvant ............................................................................................... 24 1.5 Motivation du projet de recherche .................................................................................. 29 1.6 Méthodologie .................................................................................................................. 30 iii 1.7 Références ....................................................................................................................... 31 Chapitre 2 : Techniques expérimentales ................................................................................... 41 2.1 Préparation des films de HNBR ...................................................................................... 41 2.2 Spectroscopie Infrarouge ................................................................................................ 42 2.3 Caractérisation électrochimique en pile bouton .............................................................. 44 2.3.1 Préparation de piles boutons .................................................................................... 44 2.3.2 Grandeurs caractéristiques d’une pile .....................................................................
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