Rechargeable Li-ion batteries and supercapacitors are the most promising electrochemical energy storage devices in terms of energy density and power density, respectively. Recently, nanostructured materials have gained enormous interest in the field of energy technology as they have special properties compared to the bulk. Commercially available Li-ion batteries, which are the most advanced among the rechargeable batteries, utilize microcrystalline transition metal oxides as cathode materials which act as lithium insertion hosts. To explore better electrochemical performance the use of nanomaterials instead of conventional materials would be an excellent alternative. High Li-ion insertion at high discharge rates causes slow Li+ transport which in turn results in concentration polarization of lithium ions within the electrode material, causing a drop in cell voltage. This eventually, leads in termination of the discharge process before realizing the maximum capacity of the electrode material being used. This problem can be addressed by decreasing the average particle size which leads to an increase in surface area of the electrode material. Nanostructured materials, because of their high surface area and large surface to volume ratio, to some extent can overcome the problem of slow diffusion of ions. Supercapacitors are electrical energy storage devices which can deliver large energy in a short time. A supercapacitor can be used as an auxiliary energy device along with a primary source such as a battery or a fuel cell to achieve power enhancement in short pulse applications. Active materials for supercapacitors are classified into three categories: (i) carbonaceous materials, (ii) conducting polymers and (iii) metal oxides. Among the materials studied over the years, metal oxides have been considered as attractive electrode materials for supercapacitors due to the following merits: variable oxidation state, good chemical and electrochemical stability, ease of preparation and handling. The performance of supercapacitors can be enhanced by moving from bulk to nanostructured materials. The theme of the thesis is to explore novel routes to synthesize nanostructured materials for Li-ion batteries and supercapacitors, and to investigate their physical and electrochemical characteristics. Chapter I is an introduction of various types of electrochemical energy systems such as battery, fuel cell and supercapacitor. A brief review is made on electrode materials for Li-ion batteries and supercapacitors, and nanostructured materials. Chapter II deals with the study of nanostrip orthorhombic V2O5 synthesized by a two-step procedure, with the formation of a vanadyl ethylene glycolate precursor and post-calcination treatment. The precursor and the final product are characterized for phase and composition by powder X-ray diffraction (XRD), infrared (IR) spectroscopy, thermal analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The morphological changes are investigated using field emission scanning electron microscopy (FE-SEM) and high resolution transmission electron microscopy (HRTEM). It is found that the individual strips have the following dimensions, length: 1.3 μm, width: 332 nm and thickness: 45 nm. The electrochemical lithium intercalation and de-intercalation of nanostrip V2O5 is investigated by cyclic voltammetry (CV), galvanostatic charge-discharge cycling, galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectroscopy. Chapter III describes the synthesis of nanoparticels of LiMn2O4 by microwave assisted hydrothermal method. The phase and purity of spinel LiMn2O4 are confirmed by powder XRD analysis. The morphological studies are carried out using FE-SEM and HRTEM. The electrochemical performance of spinel LiMn2O4 is studied by using CV and galvanostatic charge-discharge cycling. The initial discharge capacity is found to be about 89 mAh g-1 at a current density of 21 mA g-1 with reasonably good cyclability. Chapter IV deals with synthesis of MoO2 nanoparticles through ethylene glycol medium and its electrochemical characterization. XRD data confirms the formation MoO2 on monoclinic phase, space group P21/c. Polygon shape of MoO2 is observed in HRTEM. MoO2 facilitates reversible insertion-extraction of Li+ ions between 0.25 to 3.0 V vs. Li/Li+. CV and galvanostatic charge-discharge cycling are conducted on this anode material to complement the electrochemical data. Chapter V reports the synthesis of nanostructured MnO2 at ambient conditions by reduction of potassium permanganate with aniline. Physical characterization is carried out to identify the phase and morphology. The as prepared MnO2 is amorphous and it contains particles of 5 to 10 nm in diameter. On annealing at a temperature > 400 °C, the amorphous MnO2 attains crystalline α-phase with a concomitant change in morphology. A gradual conversion of nanoparticles to nanorods (length 500-750 nm and diameter 50-100 nm) is evident from SEM and TEM studies. High resolution TEM images suggest that nanoparticles and nanorods grow in different crystallographic planes. The electrochemical lithium intercalation and de-intercalation of nanorods was performed by (CV) and galvanostatic charge-discharge cycling. The initial discharge capacity of nanorod α-MnO2 is found to be about 197 mAh g-1 at a current density of 13.0 mA g-1. Capacitance behavior of amorphous MnO2 is studied by CV and galvanostatic charge-discharge cycling in a potential range from -0.2 to 1.0 V vs. SCE in 0.1 M sodium sulphate solution. The effect of annealing on specific capacitance is also investigated. Specific capacitance of about 250 F g-1 is obtained for as prepared MnO2 at a current density of 0.5 mA cm-2 (0.8 A g-1). Chapter VI pertains to electrochemical supercapacitor studies on nanostructured MnO2 synthesized by polyol method. Although X-ray diffraction (XRD) pattern of the as synthesized nano-MnO2 shows poor crystallinity, it is found that it is locally arranged in δ-MnO2 type layered structure composed of edge-shared network of MnO6 octahedra by Mn K-edge X-ray Absorption Near Edge Structure (XANES) measurement. Annealed MnO2 shows high crystalline tunneled based α-MnO2 as confirmed by powder XRD pattern and XANES. As synthesized MnO2 exhibits good cyclability as an electrode material for supercapacitor. In Chapter VII, capacitance behavior of nanostrip V2O5, TiO2 coated V2O5 and nanocomposites of PEDOT/V2O5 are presented. Structural and morphological studies are carried out by powder XRD, IR, TGA, SEM and TEM. Cyclic voltammogram of pristine V2O5 shows the regular rectangular shape indicating the ideal capacitance behavior in aqueous 0.1 M K2SO4. The SC value of pristine V2O5 is found to be about 100 F g-1. Nanostrip V2O5 is modified with TiO2 using titanium isobutoxide to enhance the capacitance retention upon cycling. Only 48 % of the initial capacitance remains in the case of pristine V2O5 after 100 cycles, while TiO2 coated V2O5 exhibits better cyclability with capacitance of 70 % of the initial capacitance. The capacitance retention is attributed to the presence of TiO2 on the surface of V2O5 which prevents the vanadium dissolution into the electrolyte. Microwave assisted hydrothermally synthesized PEDOT/V2O5 nanocomposites are utilized as capacitor materials. The initial SC of PEDOT/V2O5 (237 F g-1) is higher than that of either pristine V2O5 or PEDOT. The enhanced electrochemical performance is attributed to synergic effect and an enhanced bi-dimensionality. Details of the above studies are described in the thesis with a conclusion at the end of each Chapter.

Metalorganic Chemical Vapour Deposition (MOCVD) is a versatile technique for the deposition of thin films of oxide materials as it offers advantages, such as deposition over large surface area, conformal coverage, selective area deposition, and a high degree of compositional control. The MOCVD process uses metalorganic (MO) complexes, such as β-diketonate and alkoxide-based complexes, as precursors. These complexes are stable and moderately volatile. Because of the direct bond between metal and oxygen, MO complexes are natural precursors for oxide coatings. As the process involves chemical reactions taking place on the substrate surface, growth of thin films by MOCVD depends on various parameters such as the chemical nature and concentration of precursors, reaction pressure, reaction temperature, and the nature of the substrate. Such a large parameter space of the CVD process, when combined with the dynamics (thermodynamics and fluid dynamics) and kinetics, makes it rather complex. This complexity allows one to make thin films of metastable phases, including amorphous materials. One of the important findings of the work is that MOCVD process is capable of making composite coatings of carbonaceous metal oxide. Manganese is multivalent and forms various stable oxides, such as MnO, Mn2O3, Mn3O4 and MnO2. There are various potential applications of manganese oxides. MnO2 is a very well studied material for its electrochemical applications in dry cells, lithium-ion batteries, and in supercapacitors. Hence, it becomes pertinent to explore the properties of thin films of manganese oxides prepared by MOCVD for various electrochemical and other applications. The thesis work is divided into two parts. Part 1 describes the synthesis of manganese complexes, their characterization, and their application to the CVD of coatings, especially those of carbonaceous MnO. Part 2 is devoted to a detailed study of electrochemical aspects of the carbonaceous MnO coatings, followed by a report on their unusual transport properties. Chapter 1 begins with a brief introduction to thin film deposition processes. In particular, the CVD process is described with reference to various parameters such as carrier gas flow, pressure, temperature and most importantly, the CVD precursor. The chapter ends with a description of the scope of the work undertaken for the present thesis. Chapter 2 deals with “Synthesis and Characterization of MO complexes”. It begins with a description of the classification of CVD precursors with the description of MO complexes such as β-diketonates, which are generally subliming crystalline solids. Manganese β-diketonate complexes are discussed in detail. Due to the multivalent nature of Mn, there are two possible complexes namely Mn(acac)2(H2O)2 and Mn(acac)3. These complexes have been synthesised and characterized (confirmed) by various techniques, such as elemental analysis (CHN), X-ray diffraction (XRD), FTIR spectroscopy, and mass spectroscopy. Thermal analysis of the complexes shows that they are suitable as MOCVD precursors. We have used Mn(acac)2(H2O)2 as a precursor in the present work. Metalorganic complexes, where metal ion is directly bonded with both nitrogen and oxygen, can be potential candidates for the precursor for oxynitrides coatings. We have therefore studied solid crystalline anthranilate complexes of various metal ions, such as Mn2+, Co2+, Cu2+ and Zn2+ and confirmed their formation. Thermal analysis shows that anthranilate complexes are fairly volatile below 250oC and decompose below 500oC. These complexes were pyrolysed in open air and in sealed tube at different temperatures, and the resulting powder product examined by XRD, SEM, EDAX and FTIR. This preliminary study shows that anthranilate complexes yield different oxides of Mn, Co and Cu under different pyrolysis conditions, with very interesting morphological features. Pyrolysis of Zn(aa)2 in a sealed tube leads to the formation of a nanocomposite of carbon and zinc oxide (wuerzite), rich in carbon, with potential for applications in catalysis. On the other hand, the pyrolysis of Zn(aa)2 in air at the same temperature leads to leads to crystalline, nanostructured zinc oxide (wuerzite). However, no attempt has been made to use these anthranilates as CVD precursors. Chapter 3 deals with “MOCVD of Manganese Oxides and their Characterization”. It begins with a brief review of various manganese oxides and their properties. This is followed by description of the CVD reactor used for the present work, together with the conditions employed for the deposition of MnOx films. Depositions have been carried out on different substrates such as SS-316, ceramic alumina and Si (111), while varying various deposition parameters, viz., substrate, reactor pressure, carrier gas (argon) flow rate, and the duration of deposition. Significantly, depositions are divided into two categories: one, carried out in argon ambient, in the absence of a supply of oxygen (or any other oxidant) and the second one, under oxygen flow, using argon as carrier gas. The films deposited in the absence of oxygen flow are thick, black in colour, and electrically conducting, indicating the presence of carbon. The growth rate follows a typical thermal pattern, with activation energy of ~ 1.7 eV. Detailed characterization by XRD, TEM/ED, Raman, FTIR and XPS (X-ray photoelectron spectroscopy) shows that these films are composed of MnO in a carbon-rich amorphous matrix. High-resolution SEM (fig. 1) reveals a fractal pattern of cauliflower morphology, comprising very fine particles (4 – 10 nm), characteristic of very large specific surface area of the film, which is confirmed by volumetric BET measurement (~2000 m2/g). We conclude that growth in argon ambient leads to a homogenous nanocomposite film of hydrated MnO in carbon-rich matrix. Thus, our study reveals that MOCVD is a novel one-step chemical method to produce homogenous composite thin films, wherein all components of the nanocomposite film emerge from the same chemical precursor. Carbon incorporation is generally avoided by empirical process design, as it is viewed as an impurity. The potential advantages of carbon incorporation are thus not examined and the composite nature of carbonaceous films not recognized in the literature. Carbonaceous nanocomposite film can be significant as an electrode in supercapacitors, as discussed in part 2 of the thesis. Chapter 3 describes films deposited under oxygen flow, which are no longer black and are highly resistive, indicating the absence of carbon in the film, as confirmed by Raman spectroscopy. XRD, FTIR and Raman spectroscopy reveal that the films obtained under oxygen flow are more crystalline than the ones obtained in the absence of oxygen flow, and that the films are generally nanocrystalline composites of two manganese oxides, such as MnO and Mn3O4. Given the context of the carbonaceous MnO films described above, chapter 4 begins with a review of electrochemical capacitors (also called supercapacitors or ultracapacitors), which are emerging as important energy storage devices. Until now, in the Mn-O system, hydrated MnO2 has been well-studied as an electrode material due to its low cost and environmental compatibility, but the low electrical conductivity of MnO2, together with irreversible redox reactions, reduces its performance. In electrochemical capacitor applications, metal-oxide/carbon composites are finding importance. Chapter 4 deals with “MnO/C Nanocomposite Coatings as Electrodes for Electrochemical Capacitor”. In this chapter, we have examined the novel EM, i.e., the hydrated MnO/C nanocomposite coating prepared by the MOCVD process on a conducting substrate (current collector) such as SS-316 as an electrode. Electrochemical measurements have been carried out for both the 3-electrode assembly (for basic aqueous electrolyte) and 2-electrode assembly (for gel polymer electrolyte) using cyclic voltammetry (CV), AC impedance and charge-discharge techniques. The studies lead to a maximum specific capacitance of 230 – 270 F/g at 1 mA/cm2 discharge current density for the MnO/C nanocomposite coating grown at 680oC. The Bode plot shows a maximum phase angle of around 74 – 82o, indicating capacitive behaviour. The MnO/C nanocomposite film shows a very small time constant (0.5 – 3 msec), which is good for high frequency applications. The pulse power figure of merit is found to be 650 – 2000 W/g. Capacitance determined for a large number of charge-discharge cycles (~20000), and at large current densities (50 mA/cm2) show promising results. The energy density (5 - 32 Wh/kg) and power density (2 – 4 kW/kg) estimated from charge-discharge data at 1 mA/cm2 shows the potential of the nanocomposite MnO/C as electrode for superior capacitor devices. Gel polymer electrolytes (GPE) offer the advantage of large electrochemical potential window due to its structural and chemical stability. Studies have been carried out to show that the MnO/C nanocomposite film is compatible with gel polymer electrolytes based on poly(methyl methacrylate) (PMMA) and poly(acrylonitrile) (PAN) with salts of magnesium triflate and magnesium perchlorate, respectively) and plasticizers (ethylene carbonate (EC) + propylene carbonate (PC)), in a 2-electrode assembly. Chapter 5 deals with “Magnetoconductance in MnO/C Nanocomposite Coatings on Alumina”. Amorphous systems, such as MnO/C composites wherein carbon is amorphous and MnO is nearly so, are highly symmetric condensed phases, which do not possess long range translational or orientational order. Disorder in the system creates Anderson localized states just above the valence band, which lead to reduced electrical conductivity. Amorphous systems show either a small negative magnetoresistance (~ 5%) or a small positive magnetoconductance (~ 7%) at very low temperatures (~ 10 K). As such, the transport properties of the MnO/C nanocomposite film have been investigated, and are reported in chapter 5. Transport and magnetotransport measurements have been made on the MnO/C nanocomposite film grown on alumina. It is found that the MnO/C nanocomposite coating exhibits a giant negative MR (22.3%) at a temperature as high as 100 K, which is unusual because pure MnO is anti-ferromagnetic and does not ordinarily show any magnetoresistance (MR), while amorphous carbon is known to show a small MR at very low temperatures (~7 K), due to weak-localization. The present results mean that a mechanism other than weak-localization plays a role in this nanocomposite material. Further study of this material is called for, which can perhaps lead to giant magnetoresistance (GMR) at room temperature in a metal-oxide/carbon nanocomposite. A summary of the work and an outlook for further research are given in the concluding chapter 6.

Phase Shifters are one of the most important building cells of the applications in microwave and millimeter-wave range, especially for communications and radar applications / to steer the main beam for electronic scanning. This thesis includes all of the stages starting from the theoretical design stage to the measurements of the phase shifters. In detail, all-pass network phase shifter configuration is used to achieve broadband and ultra wide-band differential phase characteristics. For these reasons, 1 to 2 GHz, 2 to 4 GHz, and 3 to 6 GHz 4-bit, 22.5&deg / phase resolution phase shifter realization with surface micromachined lumped components are designed, simulated, fabricated and measured. Basic building blocks of the phase shifters, i.e., surface micromachined lumped components, square planar spiral inductors and Metal-Insulator-Metal capacitors are designed with EM simulation and lumped equivalent model extractions. The validation of the designed square planar spiral inductors is done with fabrication and measurement steps, very low error, below 1%, between the designs and fabricated samples are observed. Using this knowledge on lumped elements finally phase shifters are designed with surface micromachined lumped components, fabricated using an in house technology provided by METU-MEMS facilities, RF MEMS group. Low phase rms error, good return and insertion loss considerations are aimed, and achieved. In addition to the main work of this thesis, a generalized theoretical calculation method for 2n-1 number of stages all-pass network phase shifters is presented for the first time in literature. A different, new, broadband, and combined phase shifter topology using two-stage all-pass filters is presented. Moreover, the implementation of this idea is proved to be practical to 3 to 6 GHz 5.625&deg / and 11.25&deg / combined phase shifter. A new approach for stage numbers other than power of 2 is indicated, which is different from what is already presented in the literature. An example practical implementation results are provided for the three-stage 4-bit 1 to 6 GHz phase shifter. Also, a small improvement in SRF of the high inductance valued inductors is achieved with the mitering of the corners of square planar spiral inductors. Comparison of the measured data between the normal inductors and mitered versions shows that the first SRF of the inductors are increased about 80 MHz, and second SRF of the inductors are increased about 200 MHz.

Carbon nanotubes (CNTs) have become a popular area of materials science research due to their outstanding material properties coupled with their small size. CNTs are expected to be included in a wide variety of applications and devices in the near future. Among these devices which are nearing mass production are electrochemical double layer (ECDL) supercapacitors. The current methods to produce CNTs are numerous, with each synthesis variable resulting in changes in the physical properties of the CNT. A wide array of studies have focused on the effects of specific synthesis conditions. This research expands on earlier work done using bulk nickel catalyst, alumina supported iron catalyst, and standard chemical vapor deposition (CVD) synthesis methods. This work also investigates the effect of an applied voltage to the CVD chamber during synthesis on the physical nature of the CNTs produced. In addition, the work analyzes a novel nickel catalyst system, and the CNTs produced using this catalyst. The results of the effects of synthesis conditions on resultant CNTs are included. Additionally, CNT based ECDL supercapacitors were manufactured and tested. Scanning electron microscope (SEM) analysis reveals that catalyst choice, catalyst thickness, synthesis temperature, and applied voltage have different results on CNT dimensions. Nanotube diameter distribution and average diameter data demonstrate the effect of each synthesis condition. Additionally, the concept of an alignment parameter is introduced in order to quantify the effect of an electric field on CNT alignment. CNT based ECDL supercapacitors testing reveals that CNTs work well as an active material when a higher purity is achieved. The molarity of the electrolyte also has an effect on the performance of CNT based ECDL supercapacitors. On the basis of this research, we conclude that CNT physical dimensions can be moderately controlled based on the choice of synthesis conditions. Also, the novel nickel catalyst system investigated in this research has potential to produce bulk quantities of CNT under specific conditions. Finally, purified CNTs are recommended as a suitable active material for ECDL supercapacitors.

In recent years, electrochemical capacitors have emerged as devices with the potential to enable major advances in electrical energy storage. Electrochemical capacitors (ECs) are akin to conventional capacitors but employ higher surface-area electrodes and thinner dielectrics to achieve larger capacitances. This helps ECs to attain energy densities greater than those of conventional capacitors and power densities greater than those of batteries. Akin to conventional capacitors, ECs also have high cycle-lives and can be charged and discharged rapidly. But ECs are yet to match the energy densities of mid to high-end batteries and fuel cells. On the basis of mechanism involved in the charge-storage process, ECs are classified as electrical double-layer capacitors (EDLCs) or pseudocapacitors. Charge storage in EDLCs and pseudocapacitors is brought about by non-faradaic and faradaic processes, respectively. Faradaic process, such as an oxidation-reduction reaction, involves the transfer of charge between electrode and electrolyte. By contrast, a non-faradaic process does not use a chemical mechanism and charges are distributed on surfaces by physical processes that do not involve any chemical reaction. ECs employ both aqueous and non-aqueous electrolytes in either liquid or solid form, the latter providing the advantages of freedom from leakage of any liquid component, compactness, reliability and large operating potential-window. In the literature, polymer electrolytes are the most widely studied solid electrolytes. Complexation of functional-groups of certain polymers with cations results in the formation of polymer-cation complexes commonly referred to as solid-polymer electrolytes (SPEs). Mixing a polymer with an alkali metal salt dissolved in an organic solvent result in the formation of a polymer gel electrolyte. Organic solvents with low molecular-weights, such as ethylene carbonate and propylene carbonate, employed in polymer gel electrolytes are commonly referred to as plasticizers. When water is used as a plasticizer, the polymer electrolyte is called a polymer hydrogel electrolyte. Part I of the thesis is directed to studies pertaining to Polymer Hydrogel Electrolytes for Electrochemical Capacitors and comprises four sections. After a brief survey of literature on polymer hydrogel electrolytes employed in ECs in Section I.1, Section I.2 of Part I describes the studies on electrochemical capacitors employing cross-linked poly (vinyl alcohol) hydrogel membrane electrolytes with varying perchloric acid dopant concentration. Acidic poly (vinyl alcohol) hydrogel membrane electrolytes (PHMEs) with different perchloric acid concentrations are prepared by cross-linking poly (vinyl alcohol) with glutaraldehyde in the presence of a protonic acid acting as a catalyst under ambient conditions. PHMEs are characterized by scanning electron microscopy and temperature-modulated differential scanning calorimetry in conjunction with relevant electrochemical techniques. An optimised electrochemical capacitor assembled employing PHME in conjunction with black pearl carbon (BPC) electrodes yields a maximum specific capacitance value of about 96 F g-1, phase angle value of about 79o and a discharge capacitance value of about 88 F g-1. Section I.3 of Part I describes the studies on cross-linked poly (vinyl alcohol)/ploy (acrylic acid) blend hydrogel electrolytes for electrochemical capacitors. Acidic poly (vinyl alcohol)/poly (acrylic acid) blend hydrogel electrolytes (BHEs) have been prepared by cross-linking poly (vinyl alcohol)/poly (acrylic acid) blend with glutaraldehyde in presence of perchloric acid. These acidic BHEs have been treated suitably to realize alkaline and neutral BHEs. Thermal characteristics and glass-transition behavior of BHEs have been followed by differential scanning calorimetry. Ionic conduction in acidic BHEs has been found to take place by Grötthus-type mechanism while polymer segmental motion mechanism is predominantly responsible for ion motion in alkaline and neutral BHEs. Ionic conductivity of BHEs has been found to range between 10-3 and 10-2 S cm-1 at 298 K. Electrochemical capacitors assembled with acidic PVA hydrogel electrolyte yield a maximum specific capacitance of about 60 and 1000 F g-1 with BPC and RuOx.xH2O/C electrodes, respectively. Section I.4 of Part I describes the studies on gelatin hydrogel electrolytes and their application to electrochemical capacitors. Gelatin hydrogel electrolytes (GHEs) with varying NaCl concentrations have been prepared by cross-linking an aqueous solution of gelatin with aqueous glutaraldehyde under ambient conditions, and characterized by scanning electron microscopy, temperature-modulated differential scanning calorimetry, cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic chronopotentiometry. Glass transition temperatures for GHEs range between 340 and 377 K depending on the dopant concentration. Ionic conductivity behavior of GHEs is studied with varying concentrations of gelatin, glutaraldehyde and NaCl, and conductivity values are found to vary between 10-3 and 10-1 S cm-1 under ambient conditions. GHEs have a potential window of about 1 V with BPC electrodes. The ionic conductivity of pristine and 0.25 N NaCl-doped GHEs follows Arrhenius behavior with activation energy values of 1.9×10-4 and 1.8×10-4 eV, respectively. Electrochemical capacitors employing GHEs in conjunction with black pearl carbon electrodes are assembled and studied. Optimal values for capacitance, phase angle, and relaxation time constant of about 81 F g-1, 75o, and 0.03 s are obtained for 3 M NaCl-doped GHE, respectively. EC with pristine GHE exhibits continuous cycle life for about 4.3 h as against 4.7 h for the electrochemical capacitor with 3 M NaCl-doped GHE. Unlike electrochemical capacitors, fuel cells do not store the charge internally but instead use a continuous supply of fuel from an external storage tank. Thus, fuel cells have the potential to solve the most challenging problem associated with the electrochemical capacitors, namely their limited energy-density. A fuel cell is an electrochemical power source with advantages of both the combustion engine and the battery. Like a combustion engine, a fuel cell will run as long as it is provided with fuel; and like a battery, fuel cells convert chemical energy directly to electrical energy. As an electrochemical power source, fuel cells are not subjected to the Carnot limitations of combustion (heat) engines. A fuel cell operates quietly and efficiently and, when hydrogen is used as a fuel, it generates only power and potable water. Thus, a fuel cell is a so called ‘zero-emission engine’. In the past, several fuel cell concepts have been tested in various laboratories but the systems that are being potentially considered for commercial developments are: (i) Alkaline Fuel Cells (AFCs), (ii) Phosphoric Acid Fuel Cells (PAFCs), (iii) Polymer Electrolyte Fuel Cells (PEFCs), (iv) Solid-Polymer-Electrolyte-Direct Methanol Fuel Cells (SPE-DMFCs), (v) Molten Carbonate Fuel Cells (MCFCs) and (vi) Solid Oxide Fuel Cells (SOFCs). Among the aforesaid systems, PEFCs that employ hydrogen as fuel are considered attractive power systems for quick start-up and ambient-temperature operations. Ironically, however, hydrogen as fuel is not available freely in the nature. Accordingly, it has to be generated from a readily available hydrogen carrying fuel such as natural gas, which needs to be reformed. But, such a process leads to generation of hydrogen with some content of carbon monoxide, which even at minuscule level is detrimental to the fuel cell performance. Pure hydrogen can be generated through water electrolysis but hydrogen thus generated needs to be stored as compressed / liquefied gas, which is cost-intensive. Therefore, certain hydrogen carrying organic fuels such as methanol, ethanol, propanol, ethylene glycol, and diethyl ether have been considered for fuelling PEFCs directly. Among these, methanol with a hydrogen content of about 13 wt. % (specific energy = 6.1 kWh kg-1) is the most attractive organic liquid. PEFCs using methanol directly as fuel are referred to as SPE-DMFCs. But SPE-DMFCs suffer from methanol crossover across the polymer electrolyte membrane, which affects the cathode performance and hence the cell performance during its operation. SPE-DMFCs also have inherent limitations of low open-circuit-potential and low electrochemical-activity. An obvious solution to the aforesaid problems is to explore other promising hydrogen carrying fuels such as sodium borohydride, which has a hydrogen content of about 11 wt. %. Such fuel cells are called direct borohydride fuel cells (DBFCs). Part II of the thesis includes studies on direct borohydride fuel cells and comprises three sections. After a brief introduction to DBFCs in section II.1, Section II.2 describes studies on an alkaline direct borohydride fuel cell with hydrogen peroxide as oxidant. A peak power density of about 150 mW cm-2 at a cell voltage of 540 mV could be achieved from the optimized DBFC operating at 70oC. Section II.3 describes studies on poly (vinyl alcohol) hydrogel membrane as electrolyte for direct borohydride fuel cells. This DBFC employs a poly (vinyl alcohol) hydrogel membrane as electrolyte, an AB5 Misch metal alloy as anode, and a gold-plated stainless steel mesh as cathode in conjunction with aqueous alkaline solution of sodium borohydride as fuel and aqueous acidified solution of hydrogen peroxide as oxidant. The performance of the PHME-based DBFC in respect of peak power outputs, ex-situ cross-over of oxidant, fuel, anolyte and catholyte across the membrane electrolytes, utilization efficiencies of fuel and oxidant as also cell performance durability under ambient conditions are compared with a similar DBFC employing a Nafion®-117 membrane electrolyte (NME). Peak power densities of about 30 and 40 mW cm-2 are observed for the DBFCs with PHME and NME, respectively. The PHME and NME-based DBFCs exhibit cell potentials of about 1.2 and 1.4 V, respectively, at a load current density of 10 mA cm-2 for 100 h. Publications of Nurul Alam Choudhury 1. Gelatin hydrogel electrolytes and their application to electrochemical supercapacitors, N. A. Choudhury, S. Sampath, and A. K. Shukla, J. Electrochem. Soc., 155 (2008) A74. 2. Cross-linked polymer hydrogel electrolytes for electrochemical capacitors, N. A. Choudhury, A. K. Shukla, S. Sampath, and S. Pitchumani, J. Electrochem. Soc., 153 (2006) A614. 3. Hydrogel-polymer electrolytes for electrochemical capacitors: an overview, N. A. Choudhury, S. Sampath, and A. K. Shukla, Energy and Environmental Science (In Press). 4. Cross-linked poly (vinyl alcohol) hydrogel membrane electrolytes with varying perchloric acid dopant concentration and their application to electrochemical capacitors, N. A. Choudhury, S. Sampath, and A. K. Shukla, J. Chem. Sc. (Submitted) 5. An alkaline direct borohydride fuel cell with hydrogen peroxide as oxidant, N. A. Choudhury, R. K. Raman, S. Sampath, and A. K. Shukla, J. Power Sources, 143 (2005) 1. 6. Poly (vinyl alcohol) hydrogel membrane as electrolyte for direct borohydride fuel cells, N. A. Choudhury, S. K. Prashant, S. Pitchumani, P. Sridhar, and A. K. Shukla, J. Chem. Sc. (Submitted). 7. A phenyl-sulfonic acid anchored carbon-supported platinum catalyst for polymer electrolyte fuel cell electrodes, G. Selvarani, A. K. Sahu, N. A. Choudhury, P. Sridhar, S. Pitchumani, and A. K. Shukla, Electrochim. Acta, 52 (2007) 4871. 8. A high-output voltage direct borohydride fuel cell, R. K. Raman, N. A. Choudhury, and A. K. Shukla, Electrochem. Solid-State Lett., 7 (2004) A 488. 9. Carbon-supported Pt-Fe alloy as a methanol-resistant oxygen-reduction catalyst for direct methanol fuel cells, A. K. Shukla, R. K. Raman, N. A. Choudhury, K. R. Priolkar, P. R. Sarode, S. Emura, and R. Kumashiro, J. Electroanal. Chem., 563 (2004) 181.

The continuously increasing demand for clean renewable energy has rekindled interest in multi-terminal high voltage direct current (HVDC) grids. Although such grids have several advantages and a great potential, their materialization has been thwarted due to the absence of HVDC breakers. In comparison with traditional alternating current (AC) breakers, they should operate and interrupt fault currents in a time frame of a few milliseconds. The aim of this thesis is focused on the design of ultra-fast electro-mechanical actuator systems suitable for such HVDC breakers.Initially, holistic multi-physics and hybrid models with different levels of complexity and computation time were developed to simulate the entire switch. These models were validated by laboratory experiments. Following a generalized analysis, in depth investigations involving simulations complemented with experiments were carried out on two of the sub-components of the switch: the ultra-fast actuator and the damper. The actuator efficiency, final speed, peak current, and maximum force were explored for different design data.The results show that models with different levels of complexity should be used to model the entire switch based on the magnitude of the impulsive forces. Deformations in the form of bending or elongation may deteriorate the efficiency of the actuator losing as much as 35%. If that cannot be avoided, then the developed first order hybrid model should be used since it can simulate the behavior of the mechanical switch with a very good accuracy. Otherwise, a model comprising of an electric circuit coupled to an electromagnetic FEM model with a simple mechanics model, is sufficient.It has been shown that using a housing made of magnetic material such as Permedyn, can boost the efficiency of an actuator by as much as 80%. In light of further optimizing the ultra-fast actuator, a robust optimization algorithm was developed and parallelized. In total, 20520 FEM models were computed successfully for a total simulation time of 7 weeks. One output from this optimization was that a capacitance of 2 mF, a charging voltage of 1100 V and 40 turns yields the highest efficiency (15%) if the desired velocity is between 10 m/s and 12 m/s.The performed studies on the passive magnetic damper showed that the Halbach arrangement gives a damping force that is two and a half times larger than oppositely oriented axially magnetized magnets. Furthermore, the 2D optimization model showed that a copper thickness of 1.5 mm and an iron tube that is 2 mm thick is the optimum damper configuration. / <p>QC 20150422</p>

Cette thèse porte sur l’intégration de condensateurs accordables à base de BaxSr1-xTiO3 (BST), pour réaliser des dispositifs radiofréquences reconfigurables destinés aux antennes de téléphones portables. L’enjeu industriel principal est d’obtenir des condensateurs avec une forte accordabilité, de faibles pertes diélectriques et de faibles courants de fuite, en jouant sur la composition chimique du matériau et en contrôlant la chimie des défauts liés aux lacunes d’oxygène. La stratégie adoptée dans cette étude pour atteindre cet objectif est de doper le BST par du Mn en substitution du Ti et par du Cu en addition. Une étude complète de ces deux cas de dopage simple, réalisée à la fois sur des céramiques et des couches minces synthétisées à partir des mêmes solutions sol-gel, a dévoilé des mécanismes différents d’amélioration des propriétés diélectriques et électriques du matériau suivant le type de dopage. La complémentarité de ces deux dopants nous a alors conduit à explorer le codopage du BST en couche mince. Une architecture originale de codopage hétérogène a été mise en place, permettant de combiner les avantages des deux voies de dopage et de s’approcher fortement des spécifications imposées par le cahier des charges industriel. / This PhD work is about integration of BaxSr1-xTiO3 (BST) based tunable capacitors, in order to perform radiofrequency reconfigurable devices for cell phone antennas. The main industrial goal is to obtain capacitors with a high tunability, low dielectric losses and low leakage currents, by playing on the chemical composition of the material and by controlling the oxygen vacancy related defect chemistry. The strategy addressed in this study to reach this objective is doping the BST by Mn in substitution of Ti or by adding Cu. A full study of each case of doping, performed on both ceramics and thin films synthesized from the same sol-gel solutions, revealed different improvement mechanisms of the dielectric and electrical properties of the material according to the type of doping. The complementarity of the two doping ways has led us to investigate codoping of BST thin films. An original architecture of heterogeneous codoping has been set up, allowing to combine the benefits of each doping way and to closely meet the industrial specifications.

Les variateurs de vitesse modernes sont exclusivement basés sur l’utilisation de moteurs triphasés alimentés par des onduleurs à modulation de largeur d’impulsion (MLI). La plupart des applications modernes de la variation de vitesse, comme les ascenseurs, les grues et les machines-outils sont caractérisées principalement par un rapport élevé entre la puissance crête et la puissance moyenne et une forte demande de freinage à la puissance nominale. Dans les variateurs de vitesse ordinaires, l’énergie de freinage, qui est de l’ordre de 30 à 50% de l’énergie consommée, est dissipé dans une résistance. Outre les problèmes « énergétiques », les interruptions et dégradations de la tension d’alimentation ainsi que la qualité du courant d’entrée et la fluctuation de la charge, sont d’autres questions à aborder et à résoudre.Le super-condensateur dédié aux applications de conversion de puissance est ainsi proposé. Un variateur de vitesse équipé avec des super-condensateurs est présenté dans la thèse. Les super-condensateurs, interconnectés par un convertisseur DC-DC sont utilisés pour stocker et ré-injecter l'énergie de freinage. De plus, le convertisseur DC-DC contrôle le courant du redresseur et la tension du bus DC. Le THD du courant d’entrée est ramené à 30%. La tension du bus DC est élevée et en permanence contrôlée et lissée indépendamment de la charge et de la variation de la tension réseau. Pour terminer, les pics de puissance peuvent être lissés. La solution présentée est analysée théoriquement et vérifiée par un ensemble de simulations et expérimentations. Les résultats sont présentés et commentés / Modern controlled electric drives are exclusively based on three-phase motors that are fed from three-phase pulse width modulated (PWM) inverters. Most of modern controlled electric drive applications, such as lifts, cranes and tooling machines are characterized by high ratio of the peak to average power, and high demand for braking at the rated power. In ordinary drives, the braking energy, which represents 30-50% of the consumed energy, is dissipated on a braking resistor. Apart from the “energetic” issue, the mains interruption and degradation, the input current quality and the load fluctuation are additional issues to be addressed and solved.The ultra-capacitor dedicated for power conversion applications has been discussed. In comparison to electrochemical batteries, the ultra-capacitors have higher power density and efficiency, longer life time and greater cycling capability. This makes the ultra-capacitor an excellent candidate for power conversion applications.A new electric drive converter equipped with the ultra-capacitor is presented in the dissertation. The ultra-capacitor with an inter-connection dc-dc converter is used to store and recover the drive braking energy. Moreover, the dc-dc converter controls the rectifier current and the dc bus voltage. The drive input current THD is reduced to 30%. The dc bus voltage is boosted and controlled constant and ripple free regardless on the load and the mains voltage variation. Moreover, the drive input peak power can be smoothed. The presented solution is theoretically analysed and verified by set of simulations and experiments. The results are presented and discussed

La diminution de la longueur de grille des transistors a été le moteur essentiel de l’évolution des circuits intégrés microélectroniques ces dernières décennies. Toutefois, cette évolution des circuits microélectroniques a entrainé une densification des lignes d’interconnexion, donc la génération de fortes pertes, des ralentissements et de la diaphonie sur les signaux transmis, ainsi qu’une augmentation de l’impédance parasite des interconnexions. Cette dernière est néfaste pour l’intégrité de l’alimentation des composants actifs présents dans le circuit. Son augmentation multiplie le risque d’apparition d’erreurs numériques conduisant au dysfonctionnement d’un système. Il est donc nécessaire de réduire l’impédance sur le réseau d’alimentation des circuits intégrés. Pour ce faire, les condensateurs de découplage sont utilisés et placés hiérarchiquement à différents étages des circuits et dans leur intégralité (PCB, package, interposeur, puce).Ces travaux de doctorat s’inscrivent dans le cadre des développements récents des nouvelles solutions d’intégration 3D en microélectronique et ils portent sur l’étude de nouvelles architectures de capacités 3D, très intégrées et à fortes valeurs (>1 nF), élaborées en profondeur dans l’interposeur silicium. Ces composants, inspirés des architectures de via traversant le silicium (TSV, Through Silicon Via), sont nommées Through Silicon Capacitors (TSC). Ils constituent un élément clef pour l’amélioration des performances des alimentations des circuits intégrés car elles pourront réduire efficacement la consommation des circuits grâce à cette intégration directe de composants passifs dans l’interposeur silicium qui sert d’étage d’accueil des puces. Ces composants tridimensionnels permettent en effet d’atteindre de grandes densités de capacité de 35 nF/mm². Les enjeux sont stratégiques pour des applications embarquées et à haut débit et plus généralement dans un environnement économique et sociétal conscient de nos limites énergétiques. De plus ces condensateurs de découplage doivent fonctionner à des fréquences atteignant 2 GHz, voire 4 GHz, qui tendent à maximiser les effets parasites préjudiciables aux performances énergétiques des alimentations. Ceci est rendu possible par l’optimisation de leur intégration et l’utilisation de couches de cuivre avec, une bonne conductivité supérieure à 45 MS/m, comme électrodes.Les technologies d’élaboration des condensateurs TSC ont été développées au sein du CEA-LETI et de STMicroelectronics. Leur comportement électrique restait jusqu’alors mal connu et leurs performances difficiles à quantifier. Les études menées dans cette thèse consistaient à modéliser ces nouveaux composants en prenant en compte les paramètres matériaux et géométriques afin de connaitre les effets parasites. Les modèles électriques établis ont été confrontés à des caractérisations électriques effectuées sur une large bande de fréquence (du DC à 40 GHz). Ainsi ce travail a permis d’optimiser une architecture de capacité et leur intégration dans un réseau d’alimentation d’un circuit intégré 3D a pu montrer leur efficacité pour des opérations de découplage. / The decrease of transistor’s gate length was the key driver of the development of microelectronic integrated circuits in recent decades. However, this development of microelectronic circuits has led to a greater density of interconnection lines, generating high losses, slowdowns and crosstalk on the transmitted signals, and an increase of the parasitic impedance of interconnections lines. The latter is detrimental to the power integrity of the active components in the circuit. Its increase increases the risk of developing numerical errors leading to a system’s malfunction. It is therefore necessary to reduce the impedance of the power distribution network of integrated circuits. To do this, the decoupling capacitors are used and placed hierarchically on different floors of the circuits and in their entirety (PCB, package, interposer, chip).These doctoral works are in the context of recent developments in new 3D integration solutions in microelectronics and they carry on studying new 3D capacitors, highly integrated, presenting high capacitance values (> 1 nF), and developed by using the depth of silicon interposeur level. Inspired from the Through Silicon Vias (TSV), these newly developed 3D capacitors are named Through Silicon Capacitors (TSC). They are a key element for improving the performance of the power integrated circuits because they can efficiently reduce the consumption of circuits thanks to their direct integration in silicon interposer which is used to stack chips. These 3D components allow tor reach high capacitance density up to 35 nF/mm². The issues are strategic for high speed embedded applications and more generally in an economic and societal environment aware of our energy limits. Moreover these decoupling capacitors must operate at frequencies up to 2 GHz or 4 GHz, which tend to maximize the parasitic effects which affect the energy efficiency of power distribution networks. This is made possible by optimizing their integration and by the use of copper layers with a good conductivity higher than 45 MS / m conductivity as electrodes.The technologies used to fabricate the TSC are developed by CEA-LETI and STMicroelectronics. The electrical behavior of those TSC remained hitherto little known and their performances difficult to quantify. The studies conducted in this thesis were to model these new components by taking into account the material and geometrical parameters in order to know the parasitic effects. The established electrical models have faced electrical characterizations carried out over a wide frequency range (DC to 40 GHz). This work allow to optimize the TSC architecture and their integration in a power distribution network (Power Distribution Network - NDS) prove that they are good candidate for decoupling operations.

Conventional 2-level inverters have been quite popular in industry for drives applications. It used pulse width modulation techniques to generate a voltage waveform with high quality. For achieving this, it had to switch at high frequencies and also the switching is between 0 and Vdc. Also additional LC filters are required before feeding to a motor. 3-phase IM is the work horse of the industry. Several speed control techniques have been established namely the V/f control technique and for high performance, vector control is adopted. An electric drive system comprises of a rectifier, inverter, a motor and a load. each module is a topic by itself. This thesis work discusses the novel inverter topologies to overcome the demerits of a conventional 2-level inverter or even the basic multilevel topologies, for an electric drive. The word ‘multilevel’ itself signifies that inverter can generate more than two levels. The idea was first originated by Nabae, Takahashi and Akagi to bring an additional voltage level so that the waveform becomes a quasi square wave. This additional voltage level brought additional benefits in terms of reduced dv/dt and requirement of low switching frequency. But this was not without any cost. The inverter structure is slightly more complicated than a 2-level and also required more devices. But the advantage it gave was superior enough to such an extent that the above topology (popularly known as NPC) has become quite popular in industry. This topology was later modified to equalize the semiconductor losses among switches by replacing the clamping diodes with controllable switches and such topologies are popularly known as Active NPCs (ANPCs) because of the replacement of diodes with active switches. 3-level flying capacitors were then introduced where the additional voltage level is provided using charged capacitors. But this capacitor voltage has to be maintained at its nominal value during the inverter operation. An additional floating capacitor, which is an electrolytic capacitor is needed for this. Increasing the number of electrolytic capacitors reduces the reliability of the inverter drive since they are the weakest link in any inverters and its count has to be kept to the minimum. By using a H-bridge cell in each of the three phases, three voltage levels can be easily obtained.This is commonly known as Cascaded H-bridge (CHB) multilevel inverter. The above three topologies have been discussed with respect to generation of three pole voltage levels and these topologies are quite suited also. A higher number of voltage levels will reduce the switching frequency even lesser and also the dv/dt. On increasing the number of levels further and further, finally the inverter need not do any PWM switching and just generating the levels is sufficient enough for a good quality waveform and also low dv/dt. But when the above topologies are scaled for more than three voltage levels, all of them suffer serious drawbacks which is briefly discussed below. The diode clamped inverter (known as NPC if it is 3-level), when extended to more than three levels suffers from the neutral point balancing issue and also the count of clamping diodes increase drastically. FC inverters, when extended beyond 3-level, the number of electrolytic capacitors increases and also balancing of these capacitors to their nominal voltages becomes complicated. In the case of multilevel CHB, when extended beyond 3-level, the requirement of isolated DC sources also increases. To generate isolated supplies, phase shifting transformer and 8, 12 or 24 pulse diode rectifier is needed which increases the weight , size and cost of the drive. Therefore its application is limited. In this thesis, the aim is to develop a novel method to develop a multilevel inverter without the drawbacks faced by the basic multilevel topologies when scaled for higher number of voltage levels. This is done through stacking the basic or hybrid combination of these basic multilevel topologies through selector switches. This method is experimentally verified by stacking two 5-level inverters through a 2-level selector switch (whose switching losses can be minimized through soft cycle commutation). This will generate nine levels.Generating 9-levels through scaling the basic topologies is disadvantageous, the comparison table is provided in the thesis. This is true for any higher voltage level generation. Each of the above 5-level inverter is developed through cascading an FC with a capacitor fed H-bridge. The device count can be reduced by making the FC-CHB module common to the selector switches by shifting the selector switches between the DC link and the common FC-CHB module. Doing so, reduces the modular feature of the drive but the device count can be reduced. The FFT plot at different frequencies of operation and the switching losses of the different modules-FC, CHB and the selector switches are also plotted for different frequencies of operation. The next step is to check whether this method can be extended to any number of stackings for generation of more voltage levels. For this, a 49-level inverter is developed in laboratory by stacking three 17-level inverters. Each of the 17-level inverter is developed by cascading an FC with three CHBs. When there are 49 levels in the pole voltage waveform, there is no need to do any regular PWM since the output waveform will be very close to a sine wave even without any PWM switching. The technique used is commonly known in literature as Nearest Level Control (NLC). This method of stacking and cascading has the advantage that the FC and the CHB modules now are of very low voltages and the switching losses can be reduced. The switching losses of the different modules are calculated and plotted for different operating frequencies in the thesis. To reduce the voltages of the modules further, a 6-phase machine has been reconfigured as a 3-phase machine, the advantage being that now the DC link voltage requirement is half of that needed earlier for the same power. This further reduces voltages of the modules by half and this allows the switches to be replaced with MOSFETs, improving the efficiency of the drive. This topology is also experimentally verified for both steady state and transient conditions. So far the research focussed on a 3-phase IM fed through a stacked MLI. It can be observed that a stacked MLI needs as many DC sources as the number of stackings. A 6-phase machine apart from reduced DC link voltage requirement, has other advantages of better fault tolerant capability and better space harmonics. They are serious contenders for applications like ship propulsion, locomotive traction, electric vehicles, more electric aircraft and other high power industrial applications. Using the unique property of a 6-phase machine that its opposite windings always draw equal and opposite current, the neutral point (NP) (formed as a result of stacking two MLIs) voltage can be balanced. It was observed that the net mid point current drawn from the mid point can be made zero in a switching interval. It was later observed that with minimal changes, the mid point current drawn from the NP can be made instantaneously zero and the NP voltage deviation is completely arrested and the topology needs only very low capacity series connected capacitors energized from a single DC link. This topology is also experimentally verified using the stacked 9-level inverter topology discussed above but now for 6-phase application and experimental results are provided in the thesis. Single DC link enables direct back to back conversion and power can be fed back to the mains at any desired power factor. All the experimental verification is done on a DSP (TMS320F28335) and FPGA (Spartan 3 XCS3200) platform. An IM is run using V/f control scheme and the above inverter topologies are used to drive the motor. The IGBTs used are SKM75GB123D for the stacked 9-level inverter in the 3-phase and 6-phase experiments. For the 49-level inverter experiment, MOSFETs-IRF260N were used. Both steady state and transient results ensure that the proposed inverter topologies are suitable for high power applications.