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Double layer capacitors owe their large capacitance to high specific surface area carbon-based electrode materials adhered to a current collector via an adhesive. However, recent studies attribute greater electrical energy storage capacity to transition metal oxides/nitrides: a new generation of electrode materials for use in super-capacitors with mixed double-layer and pseudo-capacitive properties. Solution precursor plasma spray deposition is a technique that allows coatings to be fabricated with fine grain sizes, high porosity levels, and high surface area; characteristics ideal for application as super-capacitor electrodes. This investigation established conditions for deposition of porous, high specific surface area α-MoO3. It further identified a two-step temperature-programmed reaction for topotactic phase transformation of the α-MoO3 deposits into high specific surface area molybdenum nitrides of higher conductivity and higher electrochemical stability window. The electrochemical behavior of molybdenum oxide/nitride deposits was also studied in order to assess their potential for use in super-capacitors.

Double layer capacitors owe their large capacitance to high specific surface area carbon-based electrode materials adhered to a current collector via an adhesive. However, recent studies attribute greater electrical energy storage capacity to transition metal oxides/nitrides: a new generation of electrode materials for use in super-capacitors with mixed double-layer and pseudo-capacitive properties. Solution precursor plasma spray deposition is a technique that allows coatings to be fabricated with fine grain sizes, high porosity levels, and high surface area; characteristics ideal for application as super-capacitor electrodes. This investigation established conditions for deposition of porous, high specific surface area α-MoO3. It further identified a two-step temperature-programmed reaction for topotactic phase transformation of the α-MoO3 deposits into high specific surface area molybdenum nitrides of higher conductivity and higher electrochemical stability window. The electrochemical behavior of molybdenum oxide/nitride deposits was also studied in order to assess their potential for use in super-capacitors.

The supercapacitor is a perspective electrical component reaching very large capacity. Currently is beeing worked on improving its parameters. These parameters are needed to test. Charging and discharging of the supercapacitor is theoretically fully reversible process. However, real supercapacitor accompanies ageing of the electrolyte and electrodes, lead to reduction of the capacity. The aim of this work is to design a device that expose supercapacitor to accelerated ageing, which will facilitate the assessment of ageing commercial and laboratory made supercapacitors.

Ce travail porte sur la modification de matrices polymères à base de fluorure de vinylidene pour permettre leur utilisation en tant que membrane séparatrice dans les supercapacités. Basé sur un procédé d‘irradiation par rayonnement γ, l‘objectif principal était la limitation du gonflement du polymère lorsqu‘il est mis en contact d‘un milieu liquide relatif à l‘application tout en gardant d‘excellentes affinités avec celui-ci. Le processus de base exploité étant la formation et la réaction des radicaux lors de l‘irradiation du polymère, une partie de la thèse a été consacrée à leur étude par résonance paramagnétique électronique (RPE). Un modèle de simulation de spectre RPE a été mis en place pour identifier et quantifier chacune des espèces radicalaires. L‘effet de la dose d‘irradiation, de la durée d‘un recuit et de la nature de la matrice polymère (homo, copolymère) sur la proportion de ces espèces et sur leur réactivité a été évalué. Un lien avec la formation d‘un réseau a été proposé. Une attention particulière a ensuite été apportée à l‘augmentation de la densité de réticulation avec le concours d‘un agent réticulant, le TAIC. Pour terminer, une stratégie de modification des propriétés de surface du PVDF a été élaborée. Elle consiste dans un premier temps à radiogreffer un polymère à la surface du PVDF puis à modifier, dans un second temps, les greffons par une chimie douce et sélective. En conclusion, les approches complémentaires développées au cours de cette thèse ont permis de comprendre la radiolyse des polymères et de mettre à profit les processus élémentaires pour développer des stratégies robustes et prometteuses de modulation des propriétés. / This work deals with the modification of VDF-based polymer induced by γ-radiation as the polymer may be used in electrochemical supercapacitors. The main objective was to limit the swelling of the fluorinated matrix with a given electrolyte while a good wetting of the polymer by the liquid was also required. As the main basic process involved in polymer radiolysis is the formation of radicals, a part of the work was dedicated to the study of such species by using Electron Spin Resonance spectroscopy. A simulation model of ESR spectra was established in order to identify and quantify each radical species. The effect of several parameters such as radiation dose, annealing time or the nature of polymer matrix on the concentration of each species where investigated. A relation with the evolution of the crosslink density of the network formed during the radiolisys was proposed. In addition, one of the key steps of this work was to study the radiation crosslinking ability of VDF-based polymers and find a way to increase the crosslink density. This was achieved by incorporating, prior to the radiation process, a radiation sensitive crosslinker: TAIC. Finally, a new strategy based on the modification of surface properties of PVDF was investigated. It consists in the radiation grafting of pentafluorstyrene onto PVDF surface followed by the chemioselective functionalization of the grafted segments. As a conclusion, the different approaches used in this thesis allowed us to understand the radiolysis of VDF-based polymers and take advantage of the elementary process involved in this type of chemistry, to build up robust and promising strategies for tuning properties.