Microinverter has become a new trend for photovoltaic (PV) grid-tie systems due to its advantages which include greater energy harvest, simplified system installation, enhanced safety, and flexible expansion. Since an individual microinverter system is typically attached to the back of a PV module, it is desirable that it has a long lifespan that can match PV modules, which routinely warrant 25 years of operation. In order to increase the life expectancy and improve the long-term reliability, electrolytic capacitors must be avoided in microinverters because they have been identified as an unreliable component. One solution to avoid electrolytic capacitors in microinverters is using a two-stage architecture, where the high voltage direct current (DC) bus can work as a double line ripple buffer. For two-stage electrolyte-free microinverters, a high boost ratio dc-dc converter is required to increase the low PV module voltage to a high DC bus voltage required to run the inverter at the second stage. New high boost ratio dc-dc converter topologies using the hybrid transformer concept are presented in this dissertation. The proposed converters have improved magnetic and device utilization. Combine these features with the converter's reduced switching losses which results in a low cost, simple structure system with high efficiency. Using the California Energy Commission (CEC) efficiency standards a 250 W prototype was tested achieving an overall system efficiency of 97.3%. The power inversion stage of electrolyte-free microinverters requires a high efficiency grid-tie inverter. A transformerless inverter topology with low electro-magnetic interference (EMI) and leakage current is presented. It has the ability to use modern superjunction MOSFETs in conjunction with zero-reverse-recovery silicon carbide (SiC) diodes to achieve ultrahigh efficiency. The performance of the topology was experimentally verified with a tested CEC efficiency of 98.6%. Due to the relatively low energy density of film capacitors compared to electrolytic counterparts, less capacitance is used on the DC bus in order to lower the cost and reduce the volume of electrolyte-free microinverters. The reduced capacitance leads to high double line ripple voltage oscillation on DC bus. If the double line oscillation propagates back into the PV module, the maximum power point tracking (MPPT) performance would be compromised. A control method which prevents the double line oscillation from going to the PV modules, thus improving the MPPT performance was proposed. Finally, a control technique using a single microcontroller with low sampling frequency was presented to effectively eliminate electrolyte capacitors in two-stage microinverters without any added penalties. The effectiveness of this control technique was validated both by simulation and experimental results. / Ph. D.

A solid electrolyte is a crucial component of any solid state battery. Polymer gel electrolytes have received increasing attention in recent years due to their high ionic conductivity, flexibility, and improved safety. However, a general tradeoff usually exists between the mechanical properties and ionic conductivity in such materials. Molecular ionic composites (MICs) are a new type of rigid polymer gel electrolyte based on ionic liquids (ILs) and a double helical rigid-rod polyamide, poly(2,2′-disulfonyl-4,4′-benzidine terephthalamide) (PBDT). MICs have high ionic conductivity, high thermal and electrochemical stability, and widely tunable and high tensile modulus even at relatively low polymer content. MICs show great promise as solid electrolytes for solid state batteries. This dissertation describes the preparation and characterization of MIC electrolyte membranes. These transparent, flexible, and tough membranes are prepared through a convenient solvent casting process. A large variety of ILs, including both hydrophilic and hydrophobic examples, are suitable to prepare MIC electrolyte membranes by adjusting the solvents used in the casting process. The prepared membranes show a biphasic internal structure consisting of a PBDT-rich “bundle” phase and an IL-rich “puddle” (interconnected fluid) phase. Similar to the bulk MIC ingots prepared previously through an interfacial ion exchange process, the MIC membranes also have high ionic conductivity and tensile modulus at low polymer content. A MIC membrane composed of 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Pyr₁₄TFSI), LiTFSI, and PBDT in a mass ratio of 8:1:1 is tested as a solid electrolyte for lithium metal batteries. This electrolyte membrane shows high ionic conductivity and high rigidity. The shear storage modulus of this MIC electrolyte membrane only decreases by 35% when heated to 200 °C from room temperature, suggesting great mechanical stability at high temperatures. The electrolyte membrane is successfully used as solid electrolyte for a Li/LiFePO₄ battery working over a large temperature range from 23 to 150 °C, and the discharge capacity retention of the cell is as high as 99% after 50 cycles at 150 °C. By replacing the IL in the MIC with a charge-neutral liquid, single-ion-conducting polymer gel electrolyte composed of PBDT and polyethylene glycol (PEG) oligomer are obtained. Similar to the MICs, these single-ion-conducting materials also have high Young’s modulus and biphasic internal structures. This study reveals that the counter ion (Li⁺ or Na⁺) of the PBDT has a major effect on both the ionic conductivity and modulus of the materials. Due to the stronger intermolecular interactions, LiPBDT-PEG demonstrates lower ionic conductivity but higher Young’s modulus. This dissertation also evaluates the viability of rigid PBDT as a polymer binder for electrodes. Aqueous solution-processed LiFePO₄ electrodes with only 3 wt% PBDT demonstrate stable cycling over 1000 cycles without obvious capacity decay, and the rate capacity of these aqueous solution-processed electrodes are comparable to the electrodes prepared with conventional poly(vinylidene difluoride) (PVDF) as the binder, suggesting PBDT can serve as a potential electrode binder for commercial applications. / A solid electrolyte is a crucial component of any solid state battery. Polymer gel electrolytes have received increasing attention in recent years due to their high ionic conductivity, flexibility, and improved safety. However, a general tradeoff usually exists between the mechanical properties and ionic conductivity in such materials. Molecular ionic composites (MICs) are a new type of rigid polymer gel electrolyte based on ionic liquids (ILs) and a double helical rigid-rod polyamide, poly(2,2′-disulfonyl-4,4′-benzidine terephthalamide) (PBDT). MICs have high ionic conductivity, high thermal and electrochemical stability, and widely tunable and high tensile modulus even at relatively low polymer content. MICs show great promise as solid electrolytes for solid state batteries. This dissertation describes the preparation and characterization of MIC electrolyte membranes. These transparent, flexible, and tough membranes are prepared through a convenient solvent casting process. A large variety of ILs, including both hydrophilic and hydrophobic examples, are suitable to prepare MIC electrolyte membranes by adjusting the solvents used in the casting process. The prepared membranes show a biphasic internal structure consisting of a PBDT-rich "bundle" phase and an IL-rich "puddle" (interconnected fluid) phase. Similar to the bulk MIC ingots prepared previously through an interfacial ion exchange process, the MIC membranes also have high ionic conductivity and tensile modulus at low polymer content. A MIC membrane composed of 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Pyr14TFSI), LiTFSI, and PBDT in a mass ratio of 8:1:1 is tested as a solid electrolyte for lithium metal batteries. This electrolyte membrane shows high ionic conductivity and high rigidity. The shear storage modulus of this MIC electrolyte membrane only decreases by 35% when heated to 200 °C from room temperature, suggesting great mechanical stability at high temperatures. The electrolyte membrane is successfully used as solid electrolyte for a Li/LiFePO4 battery working over a large temperature range from 23 to 150 °C, and the discharge capacity retention of the cell is as high as 99% after 50 cycles at 150 °C. By replacing the IL in the MIC with a charge-neutral liquid, single-ion-conducting polymer gel electrolyte composed of PBDT and polyethylene glycol (PEG) oligomer are obtained. Similar to the MICs, these single-ion-conducting materials also have high Young's modulus and biphasic internal structures. This study reveals that the counter ion (Li+ or Na+) of the PBDT has a major effect on both the ionic conductivity and modulus of the materials. Due to the stronger intermolecular interactions, LiPBDT-PEG demonstrates lower ionic conductivity but higher Young's modulus. This dissertation also evaluates the viability of rigid PBDT as a polymer binder for electrodes. Aqueous solution-processed LiFePO4 electrodes with only 3 wt% PBDT demonstrate stable cycling over 1000 cycles without obvious capacity decay, and the rate capacity of these aqueous solution-processed electrodes are comparable to the electrodes prepared with conventional poly(vinylidene difluoride) (PVDF) as the binder, suggesting PBDT can serve as a potential electrode binder for commercial applications. / Doctor of Philosophy / Solid state batteries are widely considered as the pathway to next-generation high performance batteries. In a solid state lithium battery, the liquid organic carbonate electrolyte is replaced with a solid electrolyte. Polymer gel electrolytes are a type of potential solid electrolyte that have been widely studied in recent decades. This dissertation describes the application of a rigid polymer in preparing polymer gel electrolytes. This highly charged and rigid polymer is a water-soluble polyamide known as PBDT with a double helical structure akin to DNA. Through a modified solvent casting process, a new type of polymer gel electrolyte, known as molecular ionic composite (MIC), is prepared using PBDT and various ionic liquids. Extra salt (which can contain lithium) can also be incorporated into the MIC membrane. This type of new polymer gel electrolyte is rigid with high tensile modulus even at high temperatures and low polymer (PBDT) content. MIC membranes are used as solid electrolytes for lithium metal batteries working over a wide temperature range from 23 to 150 °C. A rigid polymer gel electrolyte can also be obtained by replacing the ionic liquids in MICs with polyethylene glycol. Besides the application in preparing solid electrolytes, PBDT is also evaluated as a polymer binder for aqueous processed electrodes. Preliminary study reveals that PBDT holds great potential for a range of commercial energy storage applications.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第25245号 / 工博第5204号 / 新制||工||1993(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 作花 哲夫, 准教授 松井 敏明 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DGAM

Low-cost, high-performance energy storage solutions are in great demand for applications such as vehicle electrification and electricity generation from renewable sources. Lithium-based batteries have emerged as strong contenders due to their high energy density and stability. However, their reliance on scarce lithium reserves and high production costs makes them impractical for many applications. Sodium-based batteries (SBBs) are gaining traction as a more affordable option, with costs of $50 to $100 per kWh and an abundant resource base. Despite these advantages, SBBs still face many obstacles, primarily due to limited research on sodium-based chemistries. Additionally, sodium-based batteries have inherent limitations, including lower energy capacity and reduced cycle life, which restrict their viability for long-term use. This thesis addresses several critical challenges faced by SBBs and explores new strategies for enhancing their performance and viability for large-scale applications. First, a low-concentration, non-flammable electrolyte consisting of 0.3 M NaPF6 in a mixed solvent was formulated and tested in SBBs. This electrolyte significantly improves the cyclability and performance of SBBs across a wide temperature range, with high-capacity retention at both elevated and sub-zero temperatures. Molecular simulations reveal that the improved ion-pairing underpins the exceptional performance. This development addresses major challenges in SBBs by offering a safer, more cost-effective solution for large-scale applications. Second, sodium-sulfur (Na-S) batteries were explored to achieve high energy densities. An external acoustic field was implemented to enhance Na-S battery performance by inhibiting the shuttle effect and reducing dendrite growth, two key challenges in Na-S systems. This method offers a scalable, non-chemical solution to improve cycle life and efficiency, making Na-S batteries a more viable candidate for large-scale energy storage. This progress, along with the high theoretical capacity of Na-S batteries, helps address the limitations not resolved by the electrolyte engineering work of SBBs. Third, the mechanisms of Na2Sx (x≤2) precipitation in sodium-sulfur (Na-S) and sodium-oxygen-sulfur (Na/O2-S) systems were investigated. The results reveal that higher-order sodium polysulfides display the lowest current density, indicating a stronger driving force is needed to initiate their reaction. In Na/(O2)-S systems, the transition from high-order to low-order oxy-sulfur intermediates demands less energy compared to Na-S systems. The insights gained here help further optimize Na-S/Na/(O2)-S batteries to enhance their performance and cycle life. Together, the work in this dissertation addressed several critical needs in the development of SBBs and helped advance their commercialization. / Doctor of Philosophy / As the demand for affordable and efficient energy storage grows, especially to support electric vehicles and electricity generation from renewable sources, new types of batteries are needed. While lithium-based batteries are commonly used due to their high energy capacity, they rely on scarce and expensive lithium resources, making them impractical for large-scale applications like storing energy for electrical grids. This has led researchers to explore sodium-based batteries, which use sodium, a much more abundant and cost-effective element. However, sodium-based batteries still face challenges, such as lower energy capacity and shorter lifespan compared to their lithium counterparts. This thesis focuses on improving sodium-based battery performance to make them a more viable option for large-scale energy storage. The first project introduces a new, safer, low-cost electrolyte that significantly enhances the performance of sodium-based batteries, even in extreme temperatures. This solution improves the battery's ability to retain its energy over multiple charging cycles, addressing some of the key issues in current sodium-based battery technology. In the second project, the focus shifts to sodium-sulfur (Na-S) batteries, which offer the potential for higher energy storage due to sulfur's high capacity. To address common issues in Na-S batteries, such as the polysulfide shuttle effect and dendrite formation, a novel acoustic approach is explored. This method reduces the migration of polysulfides between the electrodes, which preserves capacity, and also suppresses the growth of dendrites on the sodium metal anode, improving both safety and battery lifespan. As a result, the efficiency and durability of Na-S batteries are significantly enhanced, bringing them closer to practical, large-scale applications. Despite these advancements, some fundamental questions remain about how sodium polysulfides form and behave inside Na-S batteries. The third project focuses on understanding the precipitation and interaction of these compounds under different conditions. Gaining insight into these processes is essential for further enhancing battery performance and ensuring long-term reliability. In conclusion, this thesis explores several innovative strategies to improve the design and performance of sodium-based batteries, which help make them more practical for large-scale energy storage applications and ultimately contribute to a more sustainable future.

In this study, the effects of electrode microstructure and electrolyte parameters on intermediate temperature solid oxide fuel cell (ITSOFC) performance were investigated using a one-dimensional SOFC model from the Pacific Northwest National Laboratory (PNNL). After a brief review of the fundamental SOFC operating processes and a literature review incorporating more advanced SOFC topics, such as electrode microstructure modeling and mixed ionic and electronic (MIEC) composite cathodes, it was determined from the PNNL benchmark results that the dominating ITSOFC losses were caused from the activation and Ohmic overpotentials. The activation overpotential was investigated through the exchange current density term, which is dependent on the cathode activation energy, the cathode porosity, and the pore size and grain size at the cathode triple phase boundary (TPB). The cathode pore size, grain size, and porosity were not integrated in the PNNL model, therefore, an analytical solution for exchange current density from Deng and Petric (2005) was utilized to optimize their effects on performance. The Ohmic loss was determined to be entirely dependent on the electrolyte ionic conductivity, and an optimal value for this conductivity was determined. Simultaneous optimization of the above parametric evaluations led to a 388 % increase in performance from the PNNL benchmark case at 600 °C. Although this was deemed successful for this project, future research should be focused on numerically quantifying and modeling the electrode microstructure in two and·three-dimensions for more accurate results, as the electrode microstructure may be highly multi-dimensional in nature.

<p dir="ltr">Lithium-ion batteries (LIBs) are integral to modern energy storage, with graphite serving as the preferred anode material due to its high conductivity, stability, and affordability. However, challenges related to irreversible initial lithium loss, electrolyte compatibility, and lithium-ion transport kinetics limit the performance and efficiency of graphite anodes. This dissertation addresses these critical issues by exploring novel approaches to enhance the functionality of graphite anodes. The first part of the research investigates the loss of lithium during the formation of the solid electrolyte interphase (SEI) on the graphite anode during the initial charge process. To counter this loss, a new method of graphite pre-SEI is introduced. By preforming SEI layers electrochemically on graphite powders, this technique improves the initial Coulombic efficiency of full cells without sacrificing active cathode material, providing a practical solution for offsetting lithium loss. The second part focuses on overcoming the limitations of traditional electrolyte systems. Graphite's tendency to exfoliate in the presence of organic solvents restricts electrolyte choices, particularly those beyond ethylene carbonate (EC)-based solvents. This chapter presents a new electrolyte design featuring nanoscale anion networks formed by concentrated lithium salts. These networks stabilize graphite by preventing solvent co-intercalation, offering new opportunities for LIBs to operate with a broader range of electrolytes while maintaining electrode integrity. The final chapter of this dissertation re-examines the conventional understanding of lithium-ion transport through the SEI. By constructing SEI-rich structures on a niobium oxide (Nb₂O₅) anode, a new mechanism of lithium transport is proposed. Contrary to the widely accepted two-step diffusion model, findings indicate that lithium transport can occur via a one-step pore diffusion process, eliminating the kinetic limitations previously associated with the SEI and enhancing fast-charging capabilities. In the fourth chapter, a surface modification on graphite surface with a electrochemically active layer is demonstrated to improve the surface diffusion of lithium and thus enhance the low-temperature performance of graphite anodes. The next chapter the high energy density V₂O₅ cathode is revisited with multi-nonmetal doping with improved cycling stability. Overall, this dissertation advances the understanding of graphite anodes in lithium-ion batteries by providing innovative solutions to SEI formation, electrolyte design, and lithium-ion transport, paving the way for more efficient and high-performance energy storage systems.</p>

Ce travail s'inscrit dans le cadre du développement de nouveaux procédés de désacidification de gaz naturel à travers l'étude thermodynamique des équilibres entre les gaz acides (CO2 et H2S) et un solvant mixte. Ce solvant résulte de la combinaison d'un solvant chimique (solution aqueuse de diéthanolamine) et d'un solvant physique (méthanol). Couplant équilibres chimique et physique, la modélisation de ces systèmes nécessite l'élaboration de modèles complexes et une large gamme de données d'équilibre liquide-vapeur. La première partie de ce travail est consacrée à l'acquisition de données expérimentales de solubilité des gaz acides dans le solvant mixte. En étendant le champ d'application d'un appareillage fonctionnant en méthode synthétique, nous avons acquis des données originales de solubilité des mélanges CO2 + H2S dans des solvants eau-diéthanolamine-méthanol. Dans la seconde partie, la modélisation simultanée des équilibres chimiques et physiques est réalisée. L'approche hétérogène développée combine le modèle NRTL-Electrolyte pour représenter la phase liquide avec l'équation d'état de Peng-Robinson pour décrire le comportement de la phase vapeur. La procédure d'ajustement des paramètres est graduelle si bien que le système complet eau-diéthanolamine-méthanol-CO2-H2S est décrit de manière prédictive, les paramètres du modèle NRTL-Electrolyte ayant été déterminés sur des systèmes inférieurs. L'effet de solvatation du méthanol est aussi mis en valeur. Nous nous sommes également intéressés au calcul des chaleurs d'absorption et à l'extension de notre modèle à d'autres alcanolamines / This work is related to the development of new processes about gas sweetening with hybrid solvents coupling a chemical one (aqueous solution of diethanolamine) with a physical one (methanol). In the liquid phase, CO2 and H2S react with diethanolamine so that the VLE description of these systems is quite complex and requires experimental data. The first part of this work is dedicated to the experimental determination of acid gases + hybrid solvent solubility data. The experimental apparatus was improved to study H2S solubility and CO2 + H2S mixtures solubility in water-diethanolamine-methanol solvents. In the second part, the simultaneous representation of chemical and phase equilibria was realised. The heterogeneous approach developed here combines the Peng-Robinson equation of state for the vapour phase with the Electrolyte-NRTL model for the liquid phase. Parameters are fitted gradually so that the entire system water-diethanolamine-methanol-CO2-H2S system is extrapolated using Electrolyte-NRTL parameters determined by fitting experimental acid gas partial pressures of lower systems. Methanol effect is also described. An original calculation of heat of absorption was also developed. We extended the use of our approach to study others alkanolamines

Dans le contexte d'un développement durable, les véhicules électriques apparaissent comme une solution incontournable dans le futur. Parmi les dernières évolutions sur les batteries, les systèmes constitués d'une électrode au lithium (technologie lithium métal) présente des performances remarquables en termes de densité d'énergie. L'inconvénient majeur de cette méthodologie est lié à la formation de dendrites lors de la recharge susceptibles d'occasionner des courts-circuits conduisant à l'explosion de la batterie. C'est dans cet axe que s'inscrit mon sujet de thèse dont l'objectif est de développer un électrolyte polymère solide présentant une conductivité ionique élevée (2.10-4 S.cm-1 à40°C) et une tenue mécanique suffisante (30 MPa) pour limiter les phénomènes de croissance dendritique. Pour cela, la polymérisation contrôlée par les nitroxydes (NMP) a été utilisée pour synthétiser des copolymères à blocs avec un bloc possédant des groupes d'oxyde d'éthylène –CH2-CH2-O- permettant la conduction des ions lithium et un bloc de polystyrène assurant la tenue mécanique de l'électrolyte final. Le bloc assurant la conduction ionique des architectures ainsi synthétisées sont constituées soit de POE sous forme linéaire soit de POE sous forme de peigne. / In the context of sustainable development, electric vehicles appear to be a major solution for the future. Among the lastest technologies, the Lithium Metal Polymer battery has presented very interesting performances in terms of energy density. The main drawback of this system is the formation of lithium dendrites during the refill of the battery that could cause short circuits leading to the explosion of the battery. The aim of my PhD is to develop a Solid Polymer Electrolyte showing a high ionic conductivity (2.10-4 S.cm-1 at 40°C) and a high mechanical strength (30 MPa) to prevent dendritic growth. For that purpose, Nitroxide Mediated Polymerization is used to synthesize block copolymers with a PEO moiety for ionic conduction –CH2-CH2-O- and polystyrene for mechanical strength. Different kind of architectures have been synthesized : block copolymer with linear PEO moiety or with grafted PEO moiety.

Afin de pallier les problèmes de sécurité posés par l'emploi d'électrolytes liquides, des batteries incorporant des électrolytes solides ont été envisagées, conduisant à des dispositifs « tout solide » de type microbatterie au lithium. Dans le cas de ces systèmes, des études concernant les phénomènes aux interfaces restent à développer, afin de comprendre les processus limitants qui se déroulent à l'échelle atomique, similairement à la formation de la SEI (« Solid Electrolyte Interface »), bien connue dans le cas de l'utilisation d'électrolytes liquides. Dans ce type de problématiques, l'apport des méthodes de la chimie calculatoire, de part leur aspect prédictif et explicatif, est incontestable. Le présent travail de thèse, en prenant pour objet d'étude l'électrolyte solide LixPOyNz, se place dans ces problématiques, en proposant l'étude fondamentale de modèles d'interfaces électrode/électrolyte. L'électrolyte considéré étant un matériau amorphe, le premier verrou à lever consiste en la recherche d'un modèle de ce système, apte à simuler les propriétés électroniques de l'électrolyte réel, constituées par des données XPS cibles. Les calculs menés, visant à la modélisation des spectres XPS, ont permis tout à la fois de proposer un modèle de l'électrolyte et de mettre en lumière l'existence d'une coordinence des atomes d'azote non considérée jusqu'alors dans l'interprétation expérimentale des données XPS. La possible existence d'atomes d'azote monovalents au sein de l'électrolyte semble confirmée par des calculs vibrationnels, thermodynamiques et cinétiques complémentaires, tandis que ce résultat permet de réviser la vision communément admise de la structuration de l'électrolyte LixPOyNz et de la diffusion des ions Li+ au sein de celui-ci. Enfin, ce modèle structural de l'électrolyte a été employé à la simulation d'une interface électrode/électrolyte (LixPOyNz/Si). Une considération particulière a notamment été apportée à l'étude de l'adsorption du modèle à la surface et de la diffusion des ions lithium au sein de l'interface. / In order to overcome the safety issues induced by the use of liquid electrolytes, Li-ion batteries involving solid electrolytes have been considered, leading to an ‘all-solid’ kind of devices, commonly called microbatteries. For such devices, studies on the limiting processes that take place at electrode/electrolyte interfaces need to be done, to understand the electrochemical phenomenons likely to occur at the atomic scale, similarly to the well-known SEI formation. In this goal, methods of computational chemistry can provide both explanatory and predictive breakthroughs. The present work takes part in those issues by intending a study of electrode/electrolyte interfaces, considering LixPOyNz as the solid electrolyte material. Owing to the amorphous structuration of this system, the first barrier to break consists in the search for a suitable model, able to reproduce its real XPS electronic properties. Modelling of XPS spectra has both lead to propose a model of the electrolyte and highlight the possible existence of a new coordinence for nitrogen atoms, up to now unconsidered experimentally. Complementary calculations of Raman spectra, thermodynamic and kinetic data tend to evidence this coordinence, leading to a refinement of the commonly considered diffusion scheme. Finally, this structural model has been used to simulate an electrode/electrolyte interface (LixPOyNz/Si), with the particular aim of studying its adsorption on the electrode and the Li-ion diffusion through the interface.

La miniaturisation des appareils électroniques et la multiplication de leurs fonctionnalités conduisent à développer des microsources d’énergie adaptées, parmi lesquelles figurent les microbatteries au lithium. Malgré leurs excellentes performances, ces systèmes de stockage électrochimique tout solide restent toutefois limités en termes de capacité surfacique. Cette caractéristique étant intrinsèquement liée aux matériaux d’électrodes, nous avons choisi de nous intéresser à des couches minces de CuO, dont la capacité volumique théorique (426 µAh .cm-2.µm-1) est sensiblement plus élevée que celle des matériaux d’intercalation utilisés jusqu’à présent. Ce matériau réagit avec le lithium selon un mécanisme particulier, dit de conversion, qui induit la formation d’un système multiphasé et nanostructuré d’une grande complexité. Dans le cadre de ce travail, la compréhension des mécanismes électrochimiques et chimiques mis en jeu au cours du cyclage de couches minces d’oxyde de cuivre (CuO) a été l’objectif majeur. Celui-ci a nécessité une caractérisation fine du matériau actif d’électrode et des interfaces générées (interfaces solide/solide et interface solide/électrolyte). Ces études ont été principalement menées à partir de la Spectroscopie Photoélectronique à Rayonnement X (XPS), de la Microscopie à Force Atomique (AFM) et d’une modélisation théorique exploitant les méthodes de la chimie quantique. Les propriétés chimiques et morphologiques des couches minces de CuO cyclées ont été corrélées à leur comportement électrochimique. Une forte influence de leur structure et de leur morphologie initiales a pu être ainsi mise en évidence / The miniaturization of electronic components and the increasing number of their functionalities lead to the development of suitable energy microsources, among which lithium microbatteries appear. Despite the excellent performances of these all-solid-state electrochemical power sources, one main limitation that remains is their surface capacity. Its value being intrinsically connected to the nature of electrode materials, we chose to focus on CuO thin films which are characterized by a theoretical volumetric capacity (426 µAh .cm-2.µm-1) in far larger than the one of conventional intercalation materials used today. Indeed, this material reacts with lithium according to a particular mechanism, referred as conversion reaction, inducing the formation of a multiphase nanostructured system with a high complexity. In the framework of this study, understanding of electrochemical and chemical mechanisms which take place during the cycling of copper oxide thin films (CuO) was the main objective. This one has required a fine characterization of the electrode active material and the generated interfaces (solid/solid interfaces and solid/electrolyte interface). These studies have been mainly carried out with X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM) and theoretical approaches based on quantum chemistry methods. The chemical and morphological properties of the cycled CuO thin films have been linked to their electrochemical behavior. An important influence of their initial structure and morphology was then evidenced.