Electrical double-layer formed at the interface between an electrode and an electrolyte has been a topic of innumerable studies. The electrical interface plays a crucial role in kinetics, mechanisms and applications in variety of electrochemical reactions. The electrical double-layer and electron-transfer reactions lead to many important applications of electrochemistry, which include energy storage devices, namely, batteries, fuel cells and supercapacitors. Electrochemical supercapacitors can withstand to higher power than batteries and deliver higher energy than the conventional electrostatic and electrolytic capacitors. A supercapacitor can be used as an auxiliary energy device along with a primary source such as a battery or a fuel cell for the purpose of power enhancement in short pulse applications. Among the various materials studied for electrochemical supercapacitors, carboneous materials, metal oxides and conducting polymers received attention. Among carboneous materials, various forms of carbon such as powders, woven cloths, felts, fibers, nanotubes etc., are frequently studied for electrochemical supercapacitors. Low cost, high porosity, higher surface area, high abundance and well established electrode fabrication technologies are the attractive features for using carboneous materials. However, specific capacitance (SC) of these materials is rather low. These electrodes store charge by electrostatic charge separation at the electrode/electrolyte interface. Electronically conducting polymers are interesting class of materials studied for supercapacitor application because of the following merits: high electronic conductivity, environmental friendliness, ease of preparation and fabrication, high stability, high capacitance and low cost. Polyaniline (PANI), polypyrrole and polythiophene are studied in this category. Transition metal oxides have attracted considerable attention as electrode materials for supercapacitors because of the following merits: variable oxidation state, good chemical and electrochemical stability, ease of preparation and handling. Hydrated RuO2 prepared by sol-gel process at low temperature has a specific capacitance as high as 720 F g-1 due to solid state pseudo faradaic reaction. However, high cost, low porosity and toxic nature limit commercialization of supercapacitors using this material. MnO2 is attractive as it is cheap, environmentally benign, its resources are abundant in nature and also it is widely used as a cathode material in batteries. An early study on capacitance behaviour of MnO2 was reported by Lee and Goodenough. Amorphous hydrous MnO2 synthesized by co-precipitation method exhibited rectangular cyclic voltammogram in various aqueous alkali salt solutions. A specific capacitance of 200 F g-1 was reported. Following this report, several reports appeared on capacitance characteristics of MnO2. According to the charge-storage mechanism reported, a specific capacitance of 1370 F g-1 is expected from MnO2. However, this value can be obtained in practice only when the mass of MnO2 is at the level of a few micrograms per cm2 area. At such a low thickness range, the utilization of the active material is high. As thin layers of MnO2 are uneconomical for practical capacitors, studies with a mass range of 0.4-0.5 mg cm-2 have been extensively reported. At this mass range, a maximum specific capacitance of about 240 F g-1 has been obtained. With an increase in mass per unit area, the specific capacitance of MnO2 decreases. The problem associated with low values of specific capacitance of thick layers of MnO2 is the following. The MnO2 deposits or coatings generally do not possess high porosity and the electrolyte cannot permeate into the coating. Only the outer layer of the electrode is exposed to the electrolyte. Consequently, the electrochemical utilization of the material decreases with an increase in thickness. Nevertheless, utilization of thick layers of the active materials is preferable for obtaining capacitance as high as possible in a given volume and area of the electrodes. Indeed, it would be ideal if specific capacitance of MnO2 is improved from its presently reported value of 240 F g-1 to a value equivalent to that of RuO2.xH2O, namely, 720 F g-1. In view of this, attempts are made to enhance specific capacitance of MnO2 by electrochemical deposition in presence of surfactants. Nanostructured MnO2 synthesized by inverse microemulsion route is also studied for electrochemical supercapacitors. The effect of crystallographic structure of MnO2 on the capacitance properties, studies on electrochemical deposition of MnO2 in acidic and neutral medium using electrochemical quartz crystal microbalance and capacitance characteristics of MnO2-polyaniline composites are also described in the thesis. Chapter 1 briefly discusses the importance of electrochemistry in energy storage and conversion, basics of electrochemical power sources, importance of MnO2, different synthetic procedures for MnO2 and its applications in energy storage and conversion in particular for electrochemical supercapacitors. Chapter 2 provides the experimental procedures and methodologies used for the studies reported in the thesis. In chapter 3, the effect of surface active agents, namely, sodium dodecyl sulphate (SDS) and Triton X-100 added to the electrolyte during electrodeposition of MnO2 on Ni substrate on capacitance properties is presented. Electrocrystallization studies show that MnO2 nucleates instantaneously under diffusion control and grows in three dimensions. The potentiodynamically prepared oxide provides higher specific capacitance than the potentiostatically and galvanostatically prepared oxides. Specific capacitance values of 310 and 355 F g-1 obtained for MnO2 electrodeposited in the presence of 100 mM SDS and 10 mM Triton X-100 are higher than the oxide electrodeposited in the absence of surfactants. Surfactant molecules adsorbed at the electrode/electrolyte interface alters structure of double-layer and kinetics of electrodeposition. Smaller particle size, greater porosity, higher specific surface area and higher efficiency of material utilization are the factors responsible for obtaining higher specific capacitance. Extended cycle-life studies indicate that the superior performance of MnO2 due to surfactants is present throughout the cycle-life tested. Chapter 4 pertains to electrochemical supercapacitor studies on nanostructured α-MnO2 synthesized by inverse microemulsion method and the effect of annealing. As synthesized nanoparticles of MnO2 was found to be in α-crystallographic structure with particles less than 50 nm size. Nanoparticles exhibited rectangular cyclic voltammograms between 0 and 1 V vs. SCE in aqueous 0.1 M Na2SO4 at sweep rates up to 100 mV s-1 due to the short diffusion path length. On annealing at different temperatures, a mixture of nanoparticles and nanorods with varying dimension is noticed. Specific capacitance of 297 F g-1 obtained during initial cycling decreases gradually on extended cycling. The capacitance loss is attributed to the increase in the resistance for intercalation/deintercalation of alkali cations into/from MnO2 lattice. MnO2 crystallizes into several crystallographic structures, namely, α-, β-, γ-, δ- and λ-structures. As these structures differ in the way MnO6 octahedra are interlinked, they possess tunnels or inter-layers with gaps of different magnitudes. Because capacitance properties are due to intercalation/deintercalation of protons or cations in MnO2, only some crystallographic structures, which possess sufficient gap to accommodate these ions, are expected to be useful for capacitance studies. The effect of crystal structure of MnO2 on its electrochemical capacitance properties is also included in chapter 4. Specific capacitance of MnO2 is found to depend strongly on the crystallographic structure, and it decreases in the following order: α ≅ δ > γ > λ > β. A specific capacitance value of 240 F g-1 is obtained for α-MnO2, whereas it is 9 F g-1 for β-MnO2. A wide (~ 4.6 Å) tunnel size and large surface area of α-MnO2 are ascribed as favorable factors for its high specific capacitance. A large interlayer separation (~7 Å) also facilitates insertion of cations in δ-MnO2 resulting in SC close to 236 F g-1. A narrow tunnel size (1.89 Å) does not allow intercalation of cations into β-MnO2. As a result, it provides very small SC. In Chapter 5, capacitance characteristics of PANI synthesized using (NH4)2S2O8, nanostructured MnO2 (α- and γ-form) and also PANI-MnO2 composites are presented. Morphology of PANI synthesized resembles the morphology of the MnO2 used as the oxidant. Electrochemical capacitance properties of PANI and composites are studied in a mixed electrolyte of 0.1 M HClO4 and 0.3 M NaClO4 between 0 and 0.75 V vs. SCE. Specific capacitance of 394 F g-1 is obtained for PANI synthesized using γ-MnO2. Chapter 6 describes the electrocatalytic behaviour of Mn3[Fe(CN)6]2 synthesized by ion-exchange reaction between MnSO4 and K3[Fe(CN)6] and the effect of annealing on its electrochemical capacitance properties. As prepared Mn3[Fe(CN)6]2 and also the sample heated at 100 oC exhibit redox couple in 0.1 M Na2SO4 electrolyte, corresponding to Fe(CN)64-/Fe(CN)63- present in the matrix. Mn3[Fe(CN)6]2 samples annealed at 150 oC and above decompose to oxides of manganese and iron, and hence exhibit capacitance characteristics in 0.1 M Na2SO4 electrolyte. A maximum specific capacitance of 129 F g-1 is obtained for Mn3[Fe(CN)6]2 annealed at 300 oC. Electrochemical quartz crystal microbalance (EQCM) investigations of kinetics of electrodeposition of MnO2 in acidic and neutral media, and capacitance behaviour are presented in chapter 7. Oxidation of Mn2+ to MnO2 is characterized by an anodic cyclic voltammetric peak both in acidic and neutral media. During the reverse sweep, however, reduction of MnO2 into Mn2+ occurs in two steps in the acidic medium and in a single step in the neutral medium. From EQCM data of mass variation during cycling, it is observed that the rate of electrodeposition of MnO2 is higher in the neutral medium than in the acidic medium. Specific capacitance of MnO2 deposited from the neutral medium is higher than that deposited from acidic medium owing to different crystallographic structures. Reversible insertion/deinsertion of hydrogen in to the layers of δ-MnO2 is observed in hydrogen evolution region. Details of the above studies are described in the thesis.

Supercapacitors are important electrochemical energy storage devices for microelectronic and telecommunication systems, electric cars, and smart grids. However, the energy densities of existing supercapacitors are still inadequate for many applications. Vanadium oxides have been studied as viable supercapacitor alternatives, with varying results. Methods are often complicated or time-consuming, and electrode fabrication often includes carbon powder and binder. The objective of this work was to study the effect of processing conditions on specific capacitance of supercapacitors based on vanadium oxides coated on carbon fiber papers. This study was conducted to form easily-fabricated compounds of vanadium oxides which could offer promise as pseudocapacitor material, and to nucleate these compounds directly onto inexpensive carbon fiber without binder. The incipient wetness impregnation technique was used to fabricate the electrodes. Electrochemical performance of the resulting electrodes was tested in a Swagelok-type electrochemical two-electrode cell, and the electrodes were characterized by XRD and SEM. Interesting nanofeatures were formed and the vanadium oxides exhibited pseudocapacitance at a respectable level.

Several approaches have been used to develop carbon nanotube (CNT) based electrochemical supercapacitors. These approaches include the following: (a) stabilization and carbonization of ternary composites of polyacrylonitrile (PAN), poly (styrene co-acrylonitrile) (SAN) copolymer, and single wall carbon nanotubes (SWNTs); (b) SWNT membranes functionalized with aryl chloride, sodium sulfonate, aryl sulfonic acid, bis(3,5-di-tert-butylphenyl)5-aminobenzene-1,3-dioate, and 4,4 -methylenedianiline; and (c) pyrrole treated SWNTs. In addition nitric acid functionalized and heat-treated SWNT membranes have been studied. The electrochemical supercapacitor behavior of these membrane electrodes has been characterized by cyclic voltammetry, constant current charging-discharging, and impedance analysis in aqueous and ionic liquid electrolytes. Long term performance of selected electrodes has been evaluated. The surface area and pore size distribution was quantified by N2 gas adsorption/desorption and correlated with capacitance performance. The surface functional groups have been characterized by X-ray photoelectron spectroscopy. CNT electrode/electrolyte interaction has been characterized using contact angle measurements. Electrolyte absorption by the electrodes has also been characterized. Carbonized PAN/SAN/SWNT ternary composites exhibit double layer capacity of over 200 μF/cm2. By comparison, the double layer capacity of classical meso-porous carbons is in the range of 10-50 μF/cm2. The capacitance of functionalized SWNTs is up to 2 times that of the control bucky paper made from unfunctionalized SWNTs. Energy density of functionalized electrodes when evaluated in an ionic liquid is as high as 28 kJ/kg. High capacitance (up to 350 F/g) was obtained for pyrrole-treated functionalized SWNT membranes in 6 M KOH. This value is almost seven times that of the control bucky paper. Correlating the capacitance with surface area and pore size distribution, it was observed that macropores (pore width greater than 50 nm) play an important role for achieving high capacitance.

<p>In this research project, nanostructured composites based on Tin dioxide (SnO2) and Titanium dioxide (TiO2) with poly-4-styrene sulfonic acid (PSSA) doped polyaniline (PANI) conducting polymer has been investigated based on their structural, electrical and electrochemical properties. The synthesis of conducting polymers and their metal oxide or composites have been carried out chemically or electrochemically according to methods modified from the literature. Layer-by-layer construction of nano-Metal Oxide/PSSA doped polyaniline composites were successfully constructed by electroanalytical methods on the surface of a glassy carbon working electrode (GCE).</p>

The present thesis is to be brought into line with the current need for alternative and sustainable approaches toward energy management and materials design. In this context, carbon in particular has become the material of choice in many fields such as energy conversion and storage. Herein, three main topics are covered: 1)An alternative synthesis strategy toward highly porous functional carbons with tunable porosity using ordinary salts as porogen (denoted as “salt templating”) 2)The one-pot synthesis of porous metal nitride containing functional carbon composites 3)The combination of both approaches, enabling the generation of highly porous composites with finely tunable properties All approaches have in common that they are based on the utilization of ionic liquids, salts which are liquid below 100 °C, as precursors. Just recently, ionic liquids were shown to be versatile precursors for the generation of heteroatom-doped carbons since the liquid state and a negligible vapor pressure are highly advantageous properties. However, in most cases the products do not possess any porosity which is essential for many applications. In the first part, “salt templating”, the utilization of salts as diverse and sustainable porogens, is introduced. Exemplarily shown for ionic liquid derived nitrogen- and nitrogen-boron-co-doped carbons, the control of the porosity and morphology on the nanometer scale by salt templating is presented. The studies within this thesis were conducted with the ionic liquids 1-Butyl-3-methyl-pyridinium dicyanamide (Bmp-dca), 1-Ethyl-3-methyl-imidazolium dicyanamide (Emim-dca) and 1 Ethyl 3-methyl-imidazolium tetracyanoborate (Emim-tcb). The materials are generated through thermal treatment of precursor mixtures containing one of the ionic liquids and a porogen salt. By simple removal of the non-carbonizable template salt with water, functional graphitic carbons with pore sizes ranging from micro- to mesoporous and surface areas up to 2000 m2g-1 are obtained. The carbon morphologies, which presumably originate from different onsets of demixing, mainly depend on the nature of the porogen salt whereas the nature of the ionic liquid plays a minor role. Thus, a structural effect of the porogen salt rather than activation can be assumed. This offers an alternative to conventional activation and templating methods, enabling to avoid multiple-step and energy-consuming synthesis pathways as well as employment of hazardous chemicals for the template removal. The composition of the carbons can be altered via the heat-treatment procedure, thus at lower synthesis temperatures rather polymeric carbonaceous materials with a high degree of functional groups and high surface areas are accessible. First results suggest the suitability of the materials for CO2 utilization. In order to further illustrate the potential of ionic liquids as carbon precursors and to expand the class of carbons which can be obtained, the ionic liquid 1-Ethyl-3-methyl-imidazolium thiocyanate (Emim-scn) is introduced for the generation of nitrogen-sulfur-co-doped carbons in combination with the already studied ionic liquids Bmp-dca and Emim-dca. Here, the salt templating approach should also be applicable eventually further illustrating the potential of salt templating, too. In the second part, a one-pot and template-free synthesis approach toward inherently porous metal nitride nanoparticle containing nitrogen-doped carbon composites is presented. Since ionic liquids also offer outstanding solubility properties, the materials can be generated through the carbonization of homogeneous solutions of an ionic liquid acting as nitrogen as well as carbon source and the respective metal precursor. The metal content and surface area are easily tunable via the initial metal precursor amount. Furthermore, it is also possible to synthesize composites with ternary nitride nanoparticles whose composition is adjustable by the metal ratio in the precursor solution. Finally, both approaches are combined into salt templating of the one-pot composites. This opens the way to the one-step synthesis of composites with tunable composition, particle size as well as precisely controllable porosity and morphology. Thereby, common synthesis strategies where the product composition is often negatively affected by the template removal procedure can be avoided. The composites are further shown to be suitable as electrodes for supercapacitors. Here, different properties such as porosity, metal content and particle size are investigated and discussed with respect to their influence on the energy storage performance. Because a variety of ionic liquids, metal precursors and salts can be combined and a simple closed-loop process including salt recycling is imaginable, the approaches present a promising platform toward sustainable materials design. / Die vorliegende Arbeit basiert auf der Notwendigkeit für eine alternative und nachhaltige Energiewirtschaft sowie alternativer Herstellungsmethoden der damit verbundenen Materialien. Hierbei kommt besonders Kohlenstoffen und kohlenstoffbasierten Systemen eine hohe Bedeutung zu. Im Rahmen der Dissertation wurden drei Ansätze verfolgt, die zu der Entwicklung alternativer Strategien zur Herstellung poröser Heteroatom-enthaltender Kohlenstoffe und deren Komposite beitragen. Die Materialien wurden des Weiteren für die CO2 Nutzung sowie Energiespeicherung in Form von Superkondensatoren getestet. Allen Materialien ist gemeinsam, dass sie ausgehend von ionischen Flüssigkeiten, Salze mit einem Schmelzpunkt unterhalb von 100 °C, als Kohlenstoffvorstufe durch Hochtemperaturverfahren hergestellt wurden. Im ersten Teil wird ein alternatives und nachhaltiges Verfahren zur Herstellung hochporöser Stickstoff und Stickstoff-Bor-haltiger Kohlenstoffe vorgestellt. Bei dieser als „Salztemplatierung“ bezeichneten Methode werden herkömmliche Salze als Porogen verwendet. Damit sind sehr hohe Oberflächen erreichbar, die neben der Porengröße und dem Porenvolumen durch die Variation der Salzspezies und Salzmenge einstellbar sind. Dies bietet gegenüber herkömmlichen Templatierungsverfahren den Vorteil, dass das Salz nach erfolgter Karbonisierung der ionischen Flüssigkeit in Anwesenheit der nicht karbonisierbaren Salzspezies einfach mit Wasser auswaschbar ist. Hierbei ist ein Recyclingprozess denkbar. Bei hohen Synthesetemperaturen werden graphitische, bei niedrigen hochfunktionalisierte, polymerartige Produkte erhalten. Letztere erwiesen sich als vielversprechende Materialien für die CO2 Nutzung. Unter Verwendung einer bisher nicht eingesetzten ionische Flüssigkeit konnte weiterhin die Einführung von Schwefel als Heteroatom ermöglicht werden. Im zweiten Teil wird eine Templat-freie Einschrittsynthese von porösen Kompositen aus Metallnitrid Nanopartikeln und Stickstoff-dotiertem Kohlenstoff vorgestellt. Die Materialien werden ausgehend von einer Lösung aus einer ionischen Flüssigkeit und einem Metallvorläufer hergestellt, wobei die ionische Flüssigkeit sowohl als Kohlenstoffvorläufer als auch als Stickstoffquelle für die Metallnitride dient. Der Metallgehalt, das Metallverhältnis in ternären Nitriden und die Oberfläche sind über den Anteil des Metallvorläufers einstellbar. Schließlich werden beide Ansätze zur Salztemplatierung von den Kompositen kombiniert. Dadurch wird die Einschrittsynthese von Kompositen mit einstellbarer Oberfläche, Zusammensetzung, Partikelgröße und Morphologie ermöglicht. Diese Materialien wurden schließlich als Elektroden für Superkondensatoren getestet und der Einfluss verschiedener Parameter auf die Leistungsfähigkeit untersucht. Aufgrund verschiedener Kombinationsmöglichkeiten von ionischen Flüssigkeiten, Metallvorläufern und Salzen, stellen die hier präsentierten Ansätze eine vielversprechende Plattform für die nachhaltige Materialsynthese dar.

Power distribution network (PDN) design was a non-existent entity during the early days of microprocessors due to the low frequency of operation. Once the switching frequencies of the microprocessors started moving towards and beyond MHz regions, the parasitic inductance of the PCB tracks and planes started playing an important role in determining the maximum voltage on a PDN. Voltage regulator module (VRM) sup-plies only the DC power for microprocessors. When the MOSFETs inside a processor switches, it consumes currents during transition time. If this current is not provided, the voltage on the supply rails can go below the specifications of the processor. For lower MHz processors few ceramic-capacitors known as ‘decoupling capacitors’ were connected between power and ground to provide this transient current demand. When the processor frequency increased beyond MHz, the number of capacitors also increased from few numbers to hundreds of them. Nowadays, the PDN is said to be comprising all components from VRM till the die location. It includes VRM, bulk capacitors, PCB power planes, capacitor mounting pads and vias, mount for the electronic package, package capacitors, die mount and internal die capacitance. So, the PDN has evolved into a very complex system over the years. A PDN should provide three distinct roles; 1) provide transient current required by the processor 2) act as a stable reference voltage for processor 3) filter out the noise currents injected by the processor. The first two are required for the correct operation of the processor. Third one is a requirement from analog or other sensitive circuits connected to the same PDN. If the noise exits the printed circuit board (PCB), it can result in conducted and radiated EMI, which can in turn result in failure of a product in EMC testing. Every PDN design starts with the calculation of a target impedance which is given as the ratio of maximum allowed ripple voltage to the maximum transient current required by the processor. The transient current is usually taken as half the average input current. The definition of target impedance assumes that the PDN is flat over the entire frequency of operation, which is true only for a resistive network. This is seldom true for a practical PDN, since it contains inductances and capacitances. Because of this, a practical PDN has an uneven impedance versus frequency envelope. Whenever two capacitors with different self resonant frequencies are connected in parallel, their equivalent impedance produces a pole between the self resonant frequencies known as antiresonance peaks. Because of this, a PDN will have phase angles associated with them. Also, these antiresonance peaks are energy reservoirs which will be excited during the normal operation of a processor by the varying currents. The transient current of a microprocessor is modeled as a gamma function, but for practical cases it can be approximated as triangular waveforms during the transition time which is normally 10% of the time period. Depending upon the micro-operations running inside the processor, the peak value of this waveform varies. This is filtered by the on-chip capacitors, package inductance and package capacitors. Due to power gating, clock gating, IO operations, matrix multiplications and magnetic memory readings the waveforms at the board will be like pulse type, and their widths are determined by these operations. In literatures, these two types of waveforms are used for PDN analysis, depending upon at which point the study is conducted. Chapter 1 introduces the need for PDN design and the main roles of a PDN. The issue of antiresonance is introduced from a PDN perspective. Different types of capacitors used on a PDN are discussed with their strengths and limitations. The general nature of the switching noise injected by a microprocessor is also discussed. This chapter discusses the thesis contributions, and the existing work related to the field. Chapter 2 introduces a new method to calculate the target impedance (Zt ) by including the phase angles of a PDN which is based on a maximum voltage calculation. This new Zt equals to conventional Zt for symmetrical triangular switching current waveforms. The value of new Zt is less than the conventional Zt for trapezoidal excitation patterns. By adding the resonance effects into this, a maximum voltage value is obtained in this chapter. The new method includes the maximum voltage produced on a PDN when multiple antiresonance peaks are present. Example simulations are provided for triangular and pulse type excitations. A measured input current wave-form for PIC16F677 microcontroller driving eight IO ports is provided to prove the assumption of pulse type waveforms. For triangular excitation waveform, the maximum voltage predicted based on the expression was ¡0.6153 V, and the simulated maximum voltage was found to be at ¡0.5412 V which is less than the predicted value. But the predicted value based on Zt method was 1.9845 V. This shows that the conventional as well as the new target impedance method leads to over estimating the maximum voltage in certain cases. This is because most of the harmonics are falling on the minimum impedance values on a PDN. If the PDN envelope is changed by temperature and component tolerances, the maximum voltage can vary. So the best option is to design with the target impedance method. When pulse current excitation was studied for a particular PDN, the maximum voltage produced was -139.39 mV. The target impedance method produced a value of -100.24 mV. The maximum voltage predicted by the equation was -237 mV. So this shows that some times the conventional target impedance method leads to under estimating the PDN voltage. From the studies, it is shown that the time domain analysis is as important as frequency domain analysis. Another important observation is that the antiresonance peaks on a PDN should be damped both in number and peak value. Chapter 3 studies the antiresonance peak suppression methods for general cases. As discussed earlier, the antiresonance peaks are produced when two capacitors with different self resonant frequencies are connected in parallel. This chapter studies the effect of magnetic coupling between the mounting loops of two capacitors in parallel. The mounting loop area contribute to the parasitic inductance of a capacitor, and it is the major contributing factor to it. Other contributing factors are equivalent series inductance (ESL) and plane spreading inductance. The ESL depends on the size and on how the internal plates of the capacitors are formed. The spreading inductance is the inductance contributed by the parts of the planes connecting the capacitor connector vias to the die connections or to other capacitor vias. If the power and ground planes are closer, the spreading inductance is lower. On one/two layer boards dedicated power/ground planes are absent. So the spreading inductance is replaced by PCB track inductances. The inductance contributed by the mounted area of the capacitor is known as mounting inductance. On one/two layer boards dedicated power/ground planes are absent. So the spreading inductance is replaced by PCB track inductances. The dependencies of various circuit parameters on antiresonance peak are studied using circuit theory. A general condition for damping the antiresonance is formulated. The antiresonance peak reduces with Q factor. The conventional critical condition for antiresonance peak damping needs modification when magnetic coupling is present between the mounting loops of two parallel unequal value capacitors. By varying the connection geometry it is possible to obtain negative and positive coupling coefficients. The connection geometries to obtain these two are shown. An example is shown for positive and negative coupling coefficient cases with simulation and experimental results. For the example discussed, RC Æ 32 - for k Æ Å0.6 and RC Æ 64 - for k Æ ¡0.6, where RC is the critical damping value and k is the magnetic coupling coefficient between the two mounting loops. The reason for this is that, the antiresonance peak impedance value is higher for negative coupling coefficient case than that for positive coupling coefficient case. Above the self resonant frequencies of both the capacitors, the equivalent impedance of the parallel capacitors become inductive. This case is studied with two equal value capacitors in parallel. It is shown that the equivalent inductance is lower for negative coupling coefficient case as compared to positive coupling coefficient case. An example is provided with simulation and experimental results. In the experimental results, parasitic inductance is observed to be 2.6 times lower for negative coupling coefficient case than that for positive coupling coefficient case. When equal value capacitors are connected in parallel, it is advantageous to use a negative coupling geometry due to this. Chapter 4 introduces a new method to damp the antiresonance peak using a magnet-ically coupled resistive loop. Reducing the Q factor is an option to suppress the peak. In this new method, the Q factor reduction is achieved by introducing losses by mag-netically coupling a resistive loop. The proposed circuit is analyzed with circuit-theory, and governing equations are obtained. The optimum value of resistance for achieving maximum damping is obtained through analysis. Simulation and experimental results are shown to validate the theory. From the experimental results approximately 247 times reduction in antiresonance peak is observed with the proposed method. Effectiveness of the new method is limited by the magnetic coupling coefficient between the two mounting loops of capacitors. The method can be further improved if the coupling coefficient can be increased at the antiresonance frequency. Chapter 5 focuses on the third objective of a PDN, that is to reduce the noise injected by the microprocessor. A new method is proposed to reduce the conducted noise from a microprocessor with switched super capacitors. The conventional switched capacitor filters are based on the concept that the flying capacitor switching at high frequency looks like a resistor at low frequency. So for using at audio frequencies the flying capacitors were switching at MHz frequencies. In this chapter the opposite of this scenario is studied; the flying capacitors are the energy storage elements of a switched capacitor converter and they switch at lower frequencies as compared to the noise frequencies. Two basic circuits (1:1 voltage conversion ratio) providing noise isolation were discussed. They have distinct steady state input current waveforms and are explained with PSPICE simulations. The inrush current through switches are capable of destroying them in a practical implementation. A practical solution was proposed using PMOS-PNP pair. The self introduced switching noise of the converter is lower when switching frequency is low and turn ON-OFF time is higher. If power metal oxide semiconductor field effect transistor (MOSFET)s are used, the turn ON and turn OFF are slow. The switching frequency can be lowered based on the voltage drop power loss. The governing equations were formulated and simulated. It is found that the switching frequency can be lowered by increasing the capacitance value without affecting the voltage drop and power loss. From the equations, it is found that the design parameters have a cyclic dependency. Noise can short through the parasitic capacitance of the switches. Two circuits were proposed to improve the noise isolation: 1) T switch 2) ¦ switch. Of these, the ¦ switch has the higher measured transfer impedance. Experimental results showed a noise reduction of (40-20) dB for the conducted frequency range of 150 kHz - 30 MHz with the proposed 1:1 switched capacitor converter. One possible improvement of this method is to combine the noise isolation with an existing switched capacitor converter (SCC) topology. The discussed example had a switching frequency of 700 Hz, and it is shown that this can isolate the switching noise in kHz and MHz regions. In a PDN there are antiresonance peaks in kHz regions. If the proposed circuit is kept close to a microprocessor, it can reduce the excitation currents of these low frequency antiresonance peaks. Chapter 6 concludes the thesis by stating the major contributions and applications of the concepts introduced in the thesis. This chapter also discusses the future scope of these concepts.

Magister Scientiae - MSc / In this research project, nanostructured composites based on Tin dioxide (SnO2) and Titanium dioxide (TiO2) with poly-4-styrene sulfonic acid (PSSA) doped polyaniline (PANI) conducting polymer has been investigated based on their structural, electrical and electrochemical properties. The synthesis of conducting polymers and their metal oxide or composites have been carried out chemically or electrochemically according to methods modified from the literature. Layer-by-layer construction of nano-Metal Oxide/PSSA doped polyaniline composites were successfully constructed by electroanalytical methods on the surface of a glassy carbon working electrode (GCE). / South Africa

Dans le but de l’intégration des supercondensateurs dans des applicationstransport, la connaissance et l’étude de leur comportement au cours du vieillissementest nécessaire. L’objectif de cette thèse est donc la compréhension et lamodélisation des phénomènes de vieillissement observés sur lessupercondensateurs. Pour cela, des méthodologies de caractérisation électriques etdes protocoles expérimentaux originaux combinant les différentes contraintes devieillissement ont été mis en oeuvre. Des mesures du courant de fuite et des tests devieillissement combinés ont été effectués. Les résultats obtenus sont présentés. Ilsont ainsi servis au développement et l’implémentation de modèles permettant le suivide l’évolution des performances des supercondensateurs avec le vieillissement. / The study of the behavior of supercapacitors during ageing is required in orderto integrate them in transportation applications. The aim of this thesis is tounderstand and model ageing phenomena observed on supercapacitors. For thispurpose, electrical characterization methodologies and original experimentalprotocols combining various constraints of ageing have been implemented.Measurements of leakage current and combined ageing tests were conducted. Theobtained results were used for developing models allowing the monitoring of theevolution of supercapacitors performance during ageing.

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