This paper reports a novel and remarkably facile approach towards vertically aligned nanosheets on three-dimensional (3D) Ni foams. Conducting polypyrrole (PPy) sheets were grown on Ni foam through the volatilization of the environmentally friendly solvent from an ethanol–water solution of pyrrole (Py), followed by the polymerization of the coated Py in ammonium persulfate (APS) solution. The PPy-decorated Ni foams and commercial activated carbon (AC) modified Ni foams were employed as the two electrodes for the assembly of flexible all-solid-state asymmetric supercapacitors. The sheet-like structure of PPy and the macroporous feature of the Ni foam, which render large electrode–electrolyte interfaces, resulted in good capacitive performance of the supercapacitors. Moreover, a high energy density of ca. 14 Wh kg−1 and a high power density of 6.2 kW kg−1 were achieved for the all-solid-state asymmetric supercapacitors due to the wide cell voltage window.

This paper reports a novel and remarkably facile approach towards vertically aligned nanosheets on three-dimensional (3D) Ni foams. Conducting polypyrrole (PPy) sheets were grown on Ni foam through the volatilization of the environmentally friendly solvent from an ethanol–water solution of pyrrole (Py), followed by the polymerization of the coated Py in ammonium persulfate (APS) solution. The PPy-decorated Ni foams and commercial activated carbon (AC) modified Ni foams were employed as the two electrodes for the assembly of flexible all-solid-state asymmetric supercapacitors. The sheet-like structure of PPy and the macroporous feature of the Ni foam, which render large electrode–electrolyte interfaces, resulted in good capacitive performance of the supercapacitors. Moreover, a high energy density of ca. 14 Wh kg−1 and a high power density of 6.2 kW kg−1 were achieved for the all-solid-state asymmetric supercapacitors due to the wide cell voltage window.

Les travaux présentés dans cette thèse concernent la modélisation, le dimensionnement et la commande d'un coffre composé de supercondensateurs et d'un convertisseur DC/DC permettant d’alimenter les auxiliaires d’un trolleybus ou les moteurs de traction lors des coupures de la ligne aérienne. Dans la première partie, nous nous sommes intéressés au dimensionnement du système destockage pour une application du type récupération de l'énergie au freinage d'un trolleybus. Les modèles directes et inverses de la chaine cinématique ont été étudiés afin de définir une stratégie de dimensionnement du coffre s'appuyant sur le plan de Ragon. La seconde partie aborde la problématique de la fiabilité de l'élément de stockage. Le but est d'évaluer les contraintes que subissent les supercondensateurs en cours de fonctionnement et de prédire le vieillissement de ces derniers. Pour ce faire, nous avons développé et validé un modèle électrothermique du coffre de supercondensateurs. Ce modèle électrothermique a également été couplé à des lois de vieillissement permettant ainsi de prendre en compte les variations paramétriques majeures de ce système. Les résultats de ce couplage montrent l'impact de la dispersion des températures à l'intérieur du coffre sur la durée de vie de chaquesupercondensateur et du système de stockage. Finalement, le contrôle du convertisseur statique (hacheur Buck/Boost) associé auxsupercondensateurs est abordé. Une étude théorique a été menée pour synthétiser des lois de commande par mode de glissement et par PI appliqués au mode élévateur du hacheur (Boost). Ces lois de commande ont été validées sur un banc de test constitué d'un hacheur réversible, d'une alimentation DC, d'une charge résistive et de huit supercondensateurs. La comparaisondes résultats expérimentaux mettre en évidence l'intérêt de la commande par mode glissant enraison de sa robustesse et de sa réactivité par rapport à une commande classique (PI). / The studies presented in this thesis concern the thermal modeling, sizing and control of a stack composed of supercapacitors and DC/DC converter that feeds the auxiliaries or traction motors of the trolleybus in the case of electrical microcuts. In the first part, we were interested in the sizing of the storage system for an application concerning the recovering braking energy of a trolleybus. Direct and inverse models of the kinematic chain were studied in order to define a design strategy based on the Ragon. The second part concerns the reliability of the storage system. The aim is to evaluate the stresses on supercapacitors during cycling and to predict the aging of the components. Toachieve this goal, we have developed and validated an electrothermal model of the stack. This model was then coupled to aging laws allowing taking into account the major parametric variation of the system. The results show the impact of the dispersion of temperatures inside the stack on the life time of each supercapacitors in the storage system. Finally, the control of the static converter (Buck/Boost converter) combined with supercapacitors is analyzed. A theoretical study was conducted to synthesize PI and sliding mode controller applied to a boost converter. This control laws has been validated on a test bench consisting of a reversible converter, a DC power supply, a resistive load and eight supercapacitors. The experimental results show the advantage of sliding mode control in terms of robustness and reactivity compared to a classical PI control.

Room temperature molten liquids are proposed to be good alternates for volatile and harmful organic compounds. They are useful in varied areas of applications ranging from synthesis, catalysis to energy storage molten electrolytes have certain unique characteristics such as low vapour pressure, reasonably high ionic conductivity, high thermal stability and wide electrochemical window. These molten liquids can be classified in to two types depending on the nature of the species present in the liquids. One, those liquids consists only of ions (e.g) conventional imidazolium based ionic liquids and other that consists of ions and solvents (e g) acetamide eutectics. Acetamide and its eutectics from room temperature molten solvents that is unique with interesting physicochemical properties. The solvent properties of molten acetamide are similar to water, with high dielectric consist of 60 at 353 k. its acid – base properties are also similar to water, and it can solublise variety of organic and inorganic compounds as well. in the present studies room temperature molten liquids consisting of acetamide as one of the components have been prepared and used for various applications. Room temperature molten electrolytes consisting of magnesium perchlorate/magnesium triflate as one of the constituents have been used for rechargeable magnesium batteries where as those consisting of zinc perchlorate /zinc triflate have been used for zinc based rechargeable batteries. Full utilization of cathode material (y-mno2) is achieved using amide-based molten liquid as electrolyte in rechargeable zinc based batteries. Ammonium nitrate/ lithium nitrate containing electrolytes have been used for electrochemical super capacitors. They have been used as solvent cum stabilizers for metallic nanochains that can be used as substrate in surface enchanced Raman scattering studies.

The studies reported in the thesis deal with surface modification of non-platinum metals by coating with electronically conducting polymers, namely, polyanilne (PANI) and polypyrrole (PPY). The oxidation of Г/I2, hydroquinone/quinine and [Fe(CN)6]3-/ [ Fe(CN)6]4-are studied by cyclic voltammetry and chronoamperometry experiments. It has been shown tht the redox reactions, which do not occur on bare stainless steel electrode, occur through electron-transfer mediated by conducting polymers. The effect of heating of polyaniline (PANI) at 80 0C on its electrochemical activity is studies. Although the thermogravimetric analysis indicates that PANI is stable at temperatures up to about 250 0C and it undergoes decomposition at higher temperatures, its intrinsic redox electrochemical activity decreases with duration of heating at a temperature as low as 80 0C . The polymer completely loses its electrochemical activity. The decrease in lectrochemical activity of PANI is attributed to an irreversible loss of water molecules. The reaction order for degradation of PANI is found to be close to unity, and a value of 1.63 X 10-4 s-1 is obtained for the rate constant. The deactivated PANI does not recover its electrochemical activity even after a prolonged treatment in acidic electrolytes. The electrodeposition of PANI is carried out by galvanostatic, potentiostatic and potentiodynamic methods. The impedance data reflect a marked difference between the PANI deposited by static and dynamic methods. Furthermore, the impedance parameters vary with the sweep rate used in potentiodynamic method. Electrochemical impedance spectra of the electrodes are analyzed using a transmission line model consisting of two rails of finite resistances. Electrochemical deposition of polyaniline (PANI) is carried out on a porous carbon substrate for supercapacitor studies. PANI deposited at 100 mV s-1 sweep rate by potentiodynamic technique on porous carbon substrate is found to possess superior capacitance properties. Capacitance values as high as 1600 F g-1 are obtained and PANI coated carbon electrodes facilitate charge-discharge current densities as hgh as 45 mA cm-2 (19.8 A g-1 ). Electrodes are found to be fairly stable over a long cycle-life, although there is some capacitance loss during the initial stages of cycling. Electrooxidation of ascorbic acid on polyaniline is studied in a fuel-cell. Ascorbic acid (H2A) is employed as fuel and polyaniline (PANI) as the catalyst. H2A is an environmentally and biologically friendly molecule. The catalyst, namely PANI does not consist of any platinum group metal, and at 70 0C , a maximum power density of 4.3 mW cm-2 is obtained at a current density of 15 mA cm-2 . Also, studies on anodically deposited RuO2 for capacitor applications are reported. Cathodic deposition of RuO2 generally produces a mixture of Ru and RuO2 . On the other hand, the anodic depsotion on SS substrates is found to produce RUO2 which is characterized with high power supercapacitance properties. A capacitance value of 274 F g-1 is obtained at a current density of 20mA cm-2 .

Energijos kaupiklių kūrimas pastaraisiais metais tapo svarbia mokslo aktualija. Elektrocheminiai kondensatoriai pasižymi didesne galia, ilgesniu savaiminio išsikrovimo laiku ir didesniu darbo ciklų skaičiumi negu tradicinės elektrocheminės baterijos. Didžiausia savitąja talpa pasižymi RuO2, tačiau jo praktinį taikymą riboja didelė kaina, todėl ieškoma pigesnių pakaitalų. Pastaraisiais metais aktyviai tiriamas kobalto oksidas. Svarbu yra surasti ekonomiškai efektyvius ir paprastus metodus, leidžiančius padidinti kobalto oksidų pseudotalpas. Darbe nustatytos elektrocheminio Co nusodinimo sąlygos, kurioms esant yra formuojama pluoštinė nanostruktūra, pasižyminti dideliu paviršiaus plotu. Anodinės poliarizacijos būdu buvo suformuoti kobalto hidro/oksido sluoksniai ir ištirta jų pseudotalpa ant skirtingų substratų: nanostruktūrinės, magnetroninės-plazminės dangos ir metalurginio Co. Pseudotalpinė kobalto hidro/oksidų elgsena buvo ištirta ciklinės voltamperometrijos metodu kartu su elektrocheminėmis kvarco kristalo svarstyklėmis (EKKM). Oksidiniai sluoksniai parodė grįžtamą redukcijos-reoksidacijos ir atitinkamą pseudotalpinę elgseną. Per kelis tūkstančius anodinių ciklų buvo parodyta, kad oksidinis sluoksnis išliko stabilus. Nustatyta, kad hidro/oksidų, suformuotų ant nanostruktūrinės Co dangos, talpa maždaug 5 kartus didesnė nei suformuotų ant metalurginio Co. Šiame darbe pasiūlytas naujas kobalto oksido formavimo būdas: sulfidinės Co(OH)2–CoS kompozicijos formavimas ir... [toliau žr. visą tekstą] / Design of high efficiency energy accumulators has recently become an important issue of science and technology. Electrochemical capacitors are distinguished for a greater power, a longer self-discharge time and a greater number of work cycles as compared to those of traditional electrochemical batteries. Effective supercapacitors are mainly produced of RuO2, which is distinguished from other metals for its nearly highest specific capacity, however its practical application is limited by its high price, therefore efforts are under way to find cheaper substitutes. Recently cobalt oxide has been intensively studied. It is important to find economically effective and simple methods which will make it possible to increase the pseudocapacities of cobalt oxides. The conditions of electrochemical cobalt deposition, under which the fiber Co nanostructure possessing a great surface area is formed, have been determined in the work. Cobalt hydro/oxide layers were formed by the anodic polarization method and their pseudocapacity was studied on various substrates: nanostructured, magnetron-sputtered coating and metallurgical cobalt. The pseudocapacitor behaviour of cobalt hydro/oxides was studied by using the cyclic voltammetry method along with electrochemical quartz crystal mocrobalance (EKKM). Oxide layers showed oxidation-reduction and corresponding pseudo-capacitor behaviour.It has been shown that the oxide layer is stable and it withstands a few thousand polarization cycles. It has... [to full text]

Design of high efficiency energy accumulators has recently become an important issue of science and technology. Electrochemical capacitors are distinguished for a greater power, a longer self-discharge time and a greater number of work cycles as compared to those of traditional electrochemical batteries. Effective supercapacitors are mainly produced of RuO2, which is distinguished from other metals for its nearly highest specific capacity, however its practical application is limited by its high price, therefore efforts are under way to find cheaper substitutes. Recently cobalt oxide has been intensively studied. It is important to find economically effective and simple methods which will make it possible to increase the pseudocapacities of cobalt oxides. The conditions of electrochemical cobalt deposition, under which the fiber Co nanostructure possessing a great surface area is formed, have been determined in the work. Cobalt hydro/oxide layers were formed by the anodic polarization method and their pseudocapacity was studied on various substrates: nanostructured, magnetron-sputtered coating and metallurgical cobalt. The pseudocapacitor behaviour of cobalt hydro/oxides was studied by using the cyclic voltammetry method along with electrochemical quartz crystal mocrobalance (EKKM). Oxide layers showed oxidation-reduction and corresponding pseudo-capacitor behaviour.It has been shown that the oxide layer is stable and it withstands a few thousand polarization cycles. It has... [to full text] / Energijos kaupiklių kūrimas pastaraisiais metais tapo svarbia mokslo aktualija. Elektrocheminiai kondensatoriai pasižymi didesne galia, ilgesniu savaiminio išsikrovimo laiku ir didesniu darbo ciklų skaičiumi negu tradicinės elektrocheminės baterijos. Didžiausia savitąja talpa pasižymi RuO2, tačiau jo praktinį taikymą riboja didelė kaina, todėl ieškoma pigesnių pakaitalų. Pastaraisiais metais aktyviai tiriamas kobalto oksidas. Svarbu yra surasti ekonomiškai efektyvius ir paprastus metodus, leidžiančius padidinti kobalto oksidų pseudotalpas. Darbe nustatytos elektrocheminio Co nusodinimo sąlygos, kurioms esant yra formuojama pluoštinė nanostruktūra, pasižyminti dideliu paviršiaus plotu. Anodinės poliarizacijos būdu buvo suformuoti kobalto hidro/oksido sluoksniai ir ištirta jų pseudotalpa ant skirtingų substratų: nanostruktūrinės, magnetroninės-plazminės dangos ir metalurginio Co. Pseudotalpinė kobalto hidro/oksidų elgsena buvo ištirta ciklinės voltamperometrijos metodu kartu su elektrocheminėmis kvarco kristalo svarstyklėmis (EKKM). Oksidiniai sluoksniai parodė grįžtamą redukcijos-reoksidacijos ir atitinkamą pseudotalpinę elgseną. Per kelis tūkstančius anodinių ciklų buvo parodyta, kad oksidinis sluoksnis išliko stabilus. Nustatyta, kad hidro/oksidų, suformuotų ant nanostruktūrinės Co dangos, talpa maždaug 5 kartus didesnė nei suformuotų ant metalurginio Co. Šiame darbe pasiūlytas naujas kobalto oksido formavimo būdas: sulfidinės Co(OH)2–CoS kompozicijos formavimas ir... [toliau žr. visą tekstą]

The thesis deals with the production and evaluation of porous carbon materials for energy storage technologies, namely super capacitors and lithium sulfur batteries. / Die Doktorarbeit befasst sich mit der Produktion und Evaluierung poröser Kohlenstoffmaterialien für die Anwendung in Energiespeichertechnologien, namentlich Superkondensatoren und Lithiumschwefelbatterien.

Philosophiae Doctor - PhD / To meet a fast-growing market demand for next generation portable electronic devices with higher performance and increased device functionalities, efficient electrical energy devices with substantially higher energy, power densities and faster recharge times such as supercapacitors are needed. The overall aim of this thesis was to synthesize nanostructured sulphonated polyaniline and transition metal single, binary and ternary mixed oxide doped nanocomposites with electro-conductive properties. These nanocomposites were anchored on activated graphitic carbon and used in design of asymmetric supercapacitors. Tantalum(IV)oxide, tantalum(IV)oxide-nickel(II)oxide, tantalum(II)oxide-manganese(III)oxide, tantalum(II)oxide-nickel(II)oxide-manganese(II,III)oxide nanoparticles were synthesised using modified sol-gel methods. These were then dispersed, individually, in acidic media through sonication and incorporated in-situ into the polymeric matrix during the oxidative chemical polymerization of aniline doped with poly(4-styrene sulphonic acid). These novel polymeric nanocomposites were characterised with FTIR, UV-visible, TEM, SEM, EDS, XRD to ascertain successful polymerization, doping, morphology and entrapment of the metal oxide nanoparticles. SECM approach curves and interrogation of CV revealed that these nanocomposites are conductive and electro-active. The cells showed good supercapacitor characteristics with high specific capacitances of 170.5 Fg⁻¹ in TaO₂- PANi-PSSA, 166.1 Fg⁻¹ in TaO₂-NiO-PANi-PSSA, 248.4 Fg-1 in TaO-Mn₂O₃-PANi- PSSA and 119.6 Fg⁻¹ in TaO-NiO-Mn₃O₄-PANi-PSSA. Their corresponding energy densities were calculated as 245.5 Whg⁻¹, 179.4 Whg⁻¹, 357.7 Whg⁻¹ and 172.3 Whg⁻¹ respectively. They also gave respective power densities of 0.50 Whg⁻¹, 0.61 Whg⁻¹, 0.57 Whg⁻¹ and 0.65 Whg⁻¹ and showed good coulombic efficiencies ranging between 77.97% and 83.19%. These materials are found to have a long cycle life and therefore good electrode materials for constructing supercapacitor cells. / National Research Foundation (NRF)

L’intégration croissante de la Génération Distribuée basée sur des sources d’énergies renouvelables présente de nouveaux défis pour le réseau électrique centralisé actuel. Le micro-réseau est une des alternatives envisagées afin d’augmenter le taux de pénétration d’énergie renouvelable et d’améliorer la qualité de l’énergie. La stabilité d’un micro-réseau est fortement sensible aux variations de puissance venant des sources d’énergie ou des charges. Dans ce contexte, un système de stockage d’énergie joue un rôle essentiel et doit satisfaire deux conditions : disposer d’une capacité de stockage importante pour adapter la production à la demande et être capable de fournir rapidement une puissance instantanée suffisante pour pallier les problèmes de qualité d’énergie. L’objectif principal de cette thèse est de concevoir et valider expérimentalement un système de conversion de puissance et l’algorithme de contrôle associé pour la gestion du stockage dans un micro-réseau afin de satisfaire les deux conditions. Suite à l’analyse de différentes technologies de stockage, on peut conclure qu’il n’y a pas de système de stockage capable de satisfaire les conditions d’énergie et de puissance en même temps. Par conséquent, l’association d’un supercondensateur et d’une batterie Redox au Vanadium dans un Système de Stockage Hybride est utilisée pour satisfaire les conditions mentionnées. Le travail de recherche est axé sur la gestion du flux d’énergie et de puissance du Système de Stockage Hybride proposé à l’aide d’un système de conversion de puissance innovant et son algorithme de commande. Un convertisseur multi-niveaux 3LNPC a été choisi pour commander en même temps les deux systèmes de stockage, en raison de faibles pertes de puissance et de distorsions harmoniques réduites en comparaison avec d’autres topologies existantes. Un algorithme de commande capable d’exploiter les limites de fonctionnement du convertisseur sur toute sa plage de fonctionnement a été conçu afin de satisfaire de manière optimale les critères spécifiés. Le fonctionnement du système de conversion et la stratégie de commande proposée ont été validés d’abord en simulation et ensuite expérimentalement en utilisant le micro-réseau installé à l’ESTIA. / The increasing penetration of Distributed Generation systems based on Renewable Energy Sources is introducing new challenges in the current centralised electric grid. The microgrid is one of the alternatives that is being analysed in order to increase the penetration level of renewable energy sources in electrical grids and improve the power quality. The microgrid stability is highly sensitive to power variations coming from the energy sources or loads. In this context, an energy storage system is essential and it must satisfy two criteria: to have a high storage capacity to adapt the generation to the demand and to be able to supply fast power variations to overcome the power quality problems that may arise. The main objective of this thesis has been to design a power conversion system and the associated control algorithm for a storage system management in order to satisfy the defined requirements, as well as to experimentally validate the proposed solution. After an analysis of different storage system technologies, it can be concluded that there is not any storage system capable of offering the energy and power requirements at the same time. Consequently, the association of a SuperCapacitor bank and a Vanadium Redox Battery is used to satisfy the mentioned requirements. This thesis has been focused on the power and energy flow management of the proposed Hybrid Energy Storage System through an innovative power conversion system and its control method. A Three-Level Neutral Point Clamped converter has been used to control at the same time the two storage systems, due to the reduced power losses and harmonic distortion compared to other existing topologies. A control algorithm that uses the operational limits of the converter in its entire operation range has been designed in order to allow selecting the best operation point according to the specified criteria. The operation of the power conversion system and the proposed control method have been first validated in simulations and then experimentally using the microgrid installed in ESTIA.