All solid state Li-ion batteries (thin film micro batteries) have become inevitable for miniaturized devices and sensors as power sources. Fabrication of electrode materials for batteries in thin film form has been carried out with the existing technologies used in semiconductor industry. In the present thesis, radio frequency (RF) sputtering has been chosen for deposition of cathode material (ceramic oxides) thin films because of several advantages such as precise thickness control and deposition of compound thin films with equivalent composition. Conventional sputtering involves fabrication of thin film using custom made pellet according to the specification of sputter gun. However several issues such as target breaking are inevitable with the pellet sputtering. To forfend the issues, powder sputtering has been implemented for the deposition of various thin film cathodes in an economically feasible approach. Optimization of various process parameters during film deposition of cathode materials LiCoO2, Li2MnO3, LiNixMnyO4, mixed oxide cathodes of LiMn2O4, LiCoO2 and TiO2 etc., have been executed successfully by the present approach to achieve optimum electrochemical performance. Thereafter the optimized process parameters would be useful for selection of cathode layers for micro battery fabrication. Chapter 1 gives a brief introduction to the Li ion and thin film solid state batteries. It also highlights the advantages of powder sputtering compared to conventional pellet sputtering. In Chapter 2, the materials used and methods employed for the fabrication of thin film electrodes and analytical characterizations have been discussed. In chapter 3, implementation of powder sputtering for the deposition of LiCoO2 thin films has been discussed. X-Ray diffraction (XRD), X-Ray photoelectron spectroscopy (XPS) and electrochemical investigations have been carried out and promising results have been achieved. Charge discharge studies delivered a discharge capacity of 64 µAh µm-1 cm-2 in the first cycle in the potential range 3.0-4.2 V vs. Li/Li+. The possible causes for the moderate cycle life performance have been discussed. Systematic investigations for RF power optimization for the deposition of Li2-xMnO3-y thin films have been carried out. Galvanostatic charge discharge studies delivered a highest discharge capacity of 139 µAh µm-1cm-2 in the potential window 2.0-3.5 V. Thereafter, effect of LMO film thickness on electrochemical performance has been studied in the thickness range 70 nm to 300 nm. Films of lower thickness delivered higher discharge capacity with good cycle life than the thicker films. These details are discussed in chapter 4. In Chapter 5, fabrication and electrochemical performance of LiNixMnyO4 thin films are presented. LMO thin films have been deposited on nickel coated stainless steel substrates. The as deposited films were annealed at 500 °C in ambient conditions. Nickel diffuses in to LMO film and results in LiNixMnyO4 (LMNO) film. These films were further characterized. Electrochemical studies were conducted up to higher potential 4.4 V resulted in discharge capacities of the order of 55 µAh µm-1cm-2. In chapter 6, electrochemical investigations of mixed oxide thin films of LiCoO2 and LiMn2O4 have been carried out. Electrochemical investigations have been carried out in the potential window 2.0–4.3 V and a discharge capacity of 24 µAh µm-1cm-2 has been achieved. In continuation, TiO2 powder was added to the former composition and the deposited films were characterized for electrochemical performance. The potential window as well as the discharge capacity enhanced after TiO2 doping. Electrochemical characterization has been carried out in the potential window 1.4–4.5 V, and a discharge capacity of 135 µAh µm-1cm-2 has been achieved. Finally chapter 7 gives overall conclusions and future directions to the continuation of the work.

Lithium-ion battery is attractive for various applications because of its high energy density. The performance of Li-ion battery is influenced by several properties of the electrode materials such as particle size, surface area, ionic and electronic conductivity, etc. Porosity is another important property of the electrode material, which influences the performance. Pores can allow the electrolyte to creep inside the particles and also facilitate volume expansion/contraction arising from intercalation/deintercalation of Li+ ions. Additionally, the rate capability and cycle-life can be enhanced. The following porous electrode materials are investigated. Poorly crystalline porous -MnO2 is synthesized by hydrothermal route from a neutral aqueous solution of KMnO4 at 180 oC and the reaction time of 24 h. On heating, there is a decrease in BET surface area and also a change in morphology from nanopetals to clusters of nanorods. As prepared MnO2 delivers a high discharge specific capacity of 275 mAh g-1 at a specific current of 40 mA g-1 (C/5 rate). Lithium rich manganese oxide (Li2MnO3) is prepared by reverse microemulsion method employing Pluronic acid (P123) as a soft template. It has a well crystalline structure with a broadly distributed mesoporosity but low surface area. However, the sample gains surface area with narrowly distributed mesoporosity and also electrochemical activity after treating in 4 M H2SO4. A discharge capacity of about 160 mAh g-1 is obtained at a discharge current of 30 mA g-1. When the acid-treated sample is heated at 300 °C, the resulting porous sample with a large surface area and dual porosity provides a discharge capacity of 240 mAh g-1 at a discharge current density of 30 mA g-1. Solid solutions of Li2MnO3 and LiMO2 (M=Mn, Ni, Co, Fe and their composites) are more attractive positive electrode materials because of its high capacity >200 mAh g-1.The solid solutions are prepared by microemulsion and polymer template route, which results in porous products. All the solid solution samples exhibit high discharge capacities with high rate capability. Porous flower-like α-Fe2O3 nanostructures is synthesized by ethylene glycol mediated iron alkoxide as an intermediate and heated at different temperatures from 300 to 700 oC. The α-Fe2O3 samples possess porosity with high surface area and deliver discharge capacity values of 1063, 1168, 1183, 1152 and 968 mAh g-1 at a specific current of 50 mA g-1 when prepared at 300, 400, 500, 600 and 700 oC, respectively. Partially exfoliated and reduced graphene oxide (PE-RGO) is prepared by thermal exfoliation of graphite oxide (GO) under normal air atmosphere at 200-500 oC. Discharge capacity values of 771, 832, 1074 and 823 mAh g -1 are obtained with current density of 30 mA g-1 at 1st cycle for PE-RGO samples prepared at 200, 300, 400 and 500 oC, respectively. The electrochemical performance improves on increasing of exfoliation temperature, which is attributed to an increase in surface area. The high rate capability is attributed to porous nature of the material. Results of these studies are presented and discussed in the thesis.

A prototype 3-dimensional (3D) anode, based on multiwall carbon nanotubes (MWCNTs), for Li-ion batteries (LIBs), with potential use in Electric Vehicles (EVs) was investigated. The unique 3D design of the anode allowed much higher areal mass density of MWCNTs as active materials, resulting in more amount of Li+ ion intake, compared to that of a conventional 2D counterpart. Furthermore, 3D amorphous Si/MWCNTs hybrid structure offered enhancement in electrochemical response (specific capacity 549 mAhg-1). Also, an anode stack was fabricated to further increase the areal or volumetric mass density of MWCNTs. An areal mass density of the anode stack 34.9 mg/cm2 was attained, which is 1,342% higher than the value for a single layer 2.6 mg/cm2. Furthermore, the binder-assisted and hot-pressed anode stack yielded the average reversible, stable gravimetric and volumetric specific capacities of 213 mAhg-1 and 265 mAh/cm3, respectively (at 0.5C). Moreover, a large-scale patterned novel flexible 3D MWCNTs-graphene-polyethylene terephthalate (PET) anode structure was prepared. It generated a reversible specific capacity of 153 mAhg-1 at 0.17C and cycling stability of 130 mAhg-1 up to 50 cycles at 1.7C.

Les Energies Marines Renouvelables (EMR) se développent aujourd’hui très vite tant au niveau de la recherche amont que de la R&D, et même des premiers démonstrateurs à la mer. Parmi ces EMR, l'énergie des vagues présente un potentiel particulièrement intéressant. Avec une ressource annuelle brute moyenne estimée à 40 kW/m au large de la côte atlantique, le littoral français est plutôt bien exposé. Mais l’exploitation à grande échelle de cette énergie renouvelable ne sera réalisable et pertinente qu'à condition d'une bonne intégration au réseau électrique (qualité) ainsi que d'une gestion et d'un dimensionnement optimisé au sens du coût sur cycle de vie. Une première solution de génération tout électrique pour un houlogénérateur a d’abord été évaluée dans le cadre de la thèse de Marie RUELLAN menée sur le site de Bretagne du laboratoire SATIE (ENS de Cachan). Ces travaux ont mis en évidence le potentiel de viabilité économique de cette chaîne de conversion et ont permis de poser la question du dimensionnement de l’ensemble convertisseur-machine et de soulever les problèmes associés à la qualité de l’énergie produite. Puis une seconde thèse a été menée par Judicaël AUBRY dans la même équipe de recherche. Elle a consisté, entre autres, en l’étude d’une première solution de traitement des fluctuations de la puissance basée sur un système de stockage par supercondensateurs. Une méthodologie de dimensionnement de l’ensemble convertisseur-machine et de gestion de l’énergie stockée fut également élaborée, mais en découplant le dimensionnement et la gestion de la production d’énergie et de ceux de son système de stockage. Le doctorant devra donc : 1. S’approprier les travaux antérieurs réalisés dans le domaine de la récupération de l’énergie des vagues ainsi que les modèles hydrodynamiques et mécaniques réalisés par notre partenaire : le LHEEA de l’Ecole Centrale de Nantes - 2. Résoudre le problème du couplage entre dimensionnement/gestion de la chaîne de conversion et dimensionnement/gestion du système de stockage. 3. Participer à la réalisation d’un banc test à échelle réduite de la chaine électrique et valider expérimentalement les modèles énergétiques du stockage et des convertisseurs statiques associés - 4. Proposer une méthodologie de dimensionnement de la chaine électrique intégrant le stockage et les lois de contrôle préalablement élaborées 5. Déterminer les gains en termes de capacités de stockage obtenus grâce à la mutualisation de la production (parc de machines) et évaluer l’intérêt d’un stockage centralisé - 6. Analyser l’impact sur le réseau d’une production houlogénérée selon divers scenarii, modèles et outils développés par tous les partenaires dans le cadre du projet QUALIPHE. L’exemple traité sera celui de l’Ile d’Yeu (en collaboration avec le SyDEV. / The work of this PhD thesis deals with the minimization of the per-kWh cost of direct-drive wave energy converter, crucial to the economic feasibility of this technology. Despite the simplicity of such a chain (that should provide a better reliability compared to indirect chain), the conversion principle uses an oscillating system (a heaving buoy for example) that induces significant power fluctuations on the production. Without precautions, such fluctuations can lead to: a low global efficiency, an accelerated aging of the fragile electrical components and a failure to respect power quality constraints. To solve these issues, we firstly study the optimization of the direct drive wave energy converter control in order to increase the global energy efficiency (from wave to grid), considering conversion losses and the limit s from the sizing of an electrical chain (maximum force and power). The results point out the effect of the prediction horizon or the mechanical energy into the objective function. Production profiles allow the study of the flicker constraint (due to grid voltage fluctuations) linked notably to the grid characteristics at the connection point. Other models have also been developed to quantify the aging of the most fragile and highly stressed components, namely the energy storage system used for power smoothing (with super capacitors or electrochemical batteries Li-ion) and power semiconductors.Finally, these aging models are used to optimize key design parameters using life-cycle analysis. Moreover, the sizing of the storage system is co-optimized with the smoothing management.