The rising use of fossil fuels and the resulting rise in environmental harm have fueled the advancement of automobiles that are fuel-efficient. A severe existential challenge facing the planet earth has given rise to hybrid electric vehicles (HEVs), which have developed from their incipient stage and are shown promise as a solution. Additionally, when needed to produce peaking power, batteries' efficiency is reduced. Instead, supercapacitors have smaller energy storage capacity but can withstand peaking power. Designing a clever method to manage the energy balance between a supercapacitor and a battery is the main goal of this research. Different topologies are used to study the battery-supercapacitor energy storage system in great detail. Nitrogen oxides (NOx), carbon monoxide (CO), hydrocarbons (HC), and other harmful gases are less released when a battery-supercapacitor energy storage system is integrated. Additionally, it can lower the load on the battery, extending its life and improving its performance in HEVs.

This thesis explores a rigorous approach to model the behaviour of an electrochemical cell. A simple planar electrochemical cell consisting of stainless steel electrodes separated by a sulfuric acid electrolyte layer is modeled from first principles. The model is a dynamic model and is valid under constant temperature conditions. The dynamic model is based on the Poisson-Nernst-Planck electrodiffusion theory and physical attributes such as the impact of nonlinear polarization, the stoichiometric reactions of the electrolyte and changes to the transport coefficients are investigated in stages. The system of partial differential equations has been solved using a finite element software package. The simulation results are compared with experimental results and discrepancies are discussed. The results suggest that the existing theory is not adequate in explaining the physics in the immediate vicinity of the electrode/electrolyte interface even though the general experimental and simulation results are in qualitative agreement with each other.

L'utilisation de l'énergie des micro-sources de production d'électricité est un concept prometteur qui consiste à récolter des sources d'énergie faible et diffuse présent dans notre environnement pour l’alimentation de systèmes autonomes. Le nombre en croissance de nouveaux appareils miniaturisés et communicants dans les domaines civils et militaires devrait accentuer le phénomène de dépendance énergétique et ouvre de nouveaux marché.Parmi les éventuelles sources d’énergies renouvelables, l’énergie solaire est la source la plus prometteuse car elle est potentiellement la plus puissante et la mieux répartie. Le développement de ces systèmes de récupération des micro-sources d’énergie passe par de faibles coûts avec substrat souple (papier,polymère) et des matériaux facilement exploitables. Après la récupération de l’énergie, il est nécessaire pour les systèmes autonomes de stocker l'électricité.Dans cet objectif, les supercondensateurs sont les candidats idéaux. En effet, Le principal avantage des supercondensateurs par rapport aux batteries est leur haute densité de puissance (la collecte rapide de l’énergie) ainsi qu'une longue durée de vie. La thèse concerne donc la fabrication d’un supercondensateur et in fine le couplage avec une cellule solaire. Les travaux concernent spécifiquement l’étude de l'oxyde de graphène (GO) synthétisé par la méthode Hummers et Marcano, de sa réduction en oxyde de graphène réduit (RGO) par les voies chimique et électrochimique et de réalisation du supercondensateur. Dans ce projet, les propriétés de l'oxyde de graphène réduit (RGO) seront optimisées lors de l'étape de réduction et le matériau sera mis en forme dans une structure sandwich (RGO/ électrolyte /RGO) ou interdigité Mots clés: Graphène,supercondensateur, oxyde de graphène, micro-source d'énergie / The use of micro-power generation energy is a promising concept that consists in harvesting low and diffuse energy sources present in our environment for the supply of autonomous systems. The growing number of new miniaturized and communicating devices in civil and military fields should accentuate the phenomenon of energy dependence and open up new markets.Among possible sources of renewable energy, solar energy is the most promising source because it is potentially the most powerful and best distributed. The development of these micro-energy recovery systems involves low costs with flexible substrate (paper, polymer) and easily exploitable materials. After energy recovery, it is necessary for the autonomous systems to store electricity.For this purpose, supercapacitors are ideal candidates. Indeed, the main advantage of supercapacitors over batteries is their high power density (fast energy collection) as well as a long cycle life. The thesis concerns the manufacture of a supercapacitor and ultimately coupling with a solar cell. The work specifically concerns the study of graphene oxide (GO) synthesized by the Hummers and Marcano methods, its reduction in reduced graphene oxide (RGO) by chemical and electrochemical routes and the realization of supercapacitor. In this project, the properties of reduced graphene oxide (RGO) will be optimized during the reduction step and the material will be shaped into a sandwich structure (RGO / electrolyte / RGO) or interdigitated.Keywords: Graphene,supercapacitor, graphene oxide,energy micro-source

archives@tulane.edu / This dissertation utilizes molecular theory and simulations to study thermodynamics of ions in electrolyte solutions of practical interest. The first half of this work focuses on two important electrochemical energy storage systems: Lithium ion batteries and supercapacitors based on carbon nanotube (CNT) forests. In lithium ion batteries, the characteristics of Li+ transport are studied in the solid electrolyte interphase of batteries. This study has potential applications in the design and theoretical testing of novel fast-charging batteries. The work on CNT supercapacitor focuses on the dependence of capacitance on pore spacing and electrode potentials. In the second half, the hydration of halides (fluoride and chloride) are studied using Quasi-chemical theory (QCT). Here, refinements in the implementation of QCT are pursued, leading to free energies that are in excellent agreement with experiments. This advancement should be helpful to address issues such as Hofmeister effects and selectivity in ion channels. / 1 / Ajay Muralidharan

Supercapacitors are one of the most important electrochemical energy storage and conversion devices, however low ionic conductivity of solid state polymer electrolytes and the poor accessibility of the ions to the active sites in the porous electrode will cause low performance for all-solid-state supercapacitors and will limit their application. The objective of the dissertation is to improve the performance of all-solid-state supercapactor by improving electrolyte conductivity and solving accessibility problem of the ions to the active sites. The low ionic conductivity (10-8 S/cm) of poly(ethylene oxide) (PEO) limits its application as an electrolyte. Since PEO is a semicrystal polymer and the ion conduction take place mainly in the amorphous regions of the PEO/Lithium salt complex, improvements in the percentage of amorphous phase in PEO or increasing the charge carrier concentration and mobility could increase the ionic conductivity of PEO electrolyte. Hot pressing along with the additions of different lithium salts, inorganic fillers and plasticizers were applied to improve the ionic conductivity of PEO polymer electrolytes. Four electrode methods were used to evaluate the conductivity of PEO based polymer electrolytes. Results show that adding certain lithium salts, inorganic fillers, and plasticizers could improve the ionic conductivity of PEO electrolytes up 10-4 S/cm. Further hot pressing treatment could improve the ionic conductivity of PEO electrolytes up to 10-3 S/cm. The conductivity improvement after hot pressing treatment is elucidated as that the spherulite crystal phase is convert into the fringed micelle crystal phase or the amorphous phase of PEO electrolytes. PEO electrolytes were added into active carbon as a binder and an ion conductor, so as to provide electrodes with not only ion conduction, but also the accessibility of ion to the active sites of electrodes. The NaI/I2 mediator was added to improve the conductivity of PEO electrolyte and provide pseudocapacitance for all-solid-state supercapacitors. Impedance, cyclic voltammetry, and gavalnostatic charge/discharge measurements were conducted to evaluate the electrochemical performance of PEO polymer electrolytes based all-solid-state supercapacitors. Results demonstrate that the conductivity of PEO electrolyte could be improved to 0.1 S/cm with a mediator concentration of 50wt%. A high conductivity in the PEO electrolyte with mediator is an indication of a high electron exchange rate between the mediator and mediator. The high electron exchange rates at mediator carbon interface and between mediator and mediator are essential in order to obtain a high response rate and high power. This automatically solves the accessibility problem. With the addition of NaI/I2 mediator, the specific capacitance increased more than 30 folds, specific power increased almost 20 folds, and specific energy increased around 10 folds. Further addition of filler to the electrodes along with the mediator could double the specific capacitor and specific power of the all-solid-state supercapacitor. The stability of the corresponded supercapacitor is good within 2000 cycles.

The core of any electric vehicle (EV) is the electric drive train, intended as the energy conversion chain from the energy tank (typically some kind of rechargeable battery) to the electric motor that converts the electrical energy into the mechanical energy needed for the vehicle motion. The need for on-board electrical energy storage is the factor that has so far prevented pure electric vehicles from conquering significant market share. In fact electrochemical batteries, which are currently the most suitable device for electrical energy storage, have serious limitations in terms of energy and/or power density, cost and safety. All those characteristics reflect in pure electric vehicles being outperformed by standard internal combustion engine (ICE) based vehicles in terms of driving range, time needed to refuel and purchase cost. Electric vehicles do have their distinctive advantages, being intrinsically much more efficient, operating at zero emissions at the pipe, and offering a higher degree of controllability that can potentially enhance driving safety. No wonder then, that electric energy storage technology has attracted considerable R&D investments, resulting in new traction battery packs that are getting closer and closer to the industrial targets. In this scenario of EV technology gaining momentum, power electronics engineers have to come up with newer solutions allowing for more efficient and more reliable utilization of the precious on-board energy that comes in a form that cannot be directly utilized by the motor. At present, most of the research in the area of power electronics for automotive is focused in volume and cost reduction techniques. The increase in power density is pursued by developing components that can be operated at higher temperature, thus relieving the requirements on cooling. In this thesis, the focus is on the development of alternative topologies for the power electronics converters that make use of some peculiarities of the energy storage components and of the electrical drive train in general, rather than being a mere component-level optimization of well established topologies. A novel converter topology is proposed for hybridization of the energy source with a supercapacitor-based power buffer being used to assist the main traction battery. From the functional point of view, the topology implements a bidirectional DC/DC converter. Making use of the fact that the battery terminal voltage is close to constant, an arrangement for the supercapacitors is devised allowing for bidirectional power flow by using power electronics devices of lower ratings than the ones needed in conventional DC/DC converters. At the same time, much smaller magnetic components are needed. Theoretical analysis of the operation of the proposed converter is given, allowing for optimized design. A full-scale experimental prototype rated at 30 kW, intended for use in a pure EV, has been built and tested. Results validate the theory and show that no particular impediment exist to the deployment of the concept in practical applications. Another concept introduced in the thesis is an architecture where the traction inverter is embedded in the energy storage device. The latter is constituted by several modules, as in the case of modern Li-ion battery systems, and each module is equipped with a local power electronics interface, making it functionally equivalent to a controllable voltage source. The result is a modular, distributed system that can be engineered to have very high reliability and also to exhibit self-healing properties. A prototype with a minimum number of modules has been built and tested. Results confirm the effectiveness of the system, and make it a good candidate for deployment in applications where reliability is the most important requirement.

This doctoral thesis gives background to the field of electrochemical energy storage in supercapacitors. It attempts to place the supercapacitor device in context of available and future technologies for alternative energy systems for transportation. Limitations of cells and electrodes and key challenges in the supercapacitor development are introduced. One objective of the thesis is to investigate and describe ionic transport in active carbon and possible restrictions in nanostructured porous systems with focus on small (micro and meso) pores. Another is to develop a model suitable for investigations of concentration and potential profiles from a single particle perspective. The results from the studies are presented in this thesis together with the scientific papers this thesis is based on. Studying electrochemical gradients (concentration and potential) of large electrodes and single particles may give important information of the limitations of the material. In larger three-electrode experimental set-ups, these gradients can be studied for electrodes but single particles are not available for experimental studies to the same extent since the matrix of an electrode consist of many particles, all adding to the total gradient of the electrode. The experimental part of this thesis is based on different experimental techniques: Three-electrode experiments for larger electrodes, microelectrode experiments for single particles, numerical simulations using Multiphysics (software) of large electrodes consisting of single particles. Four Papers are appended to the thesis. They present results and discussions regarding ionic transport, surface functionalities and modeling of a particle based supercapacitor electrode. Estimated effective diffusivities for an active carbon containing micro, meso and macropores are presented. Surface functionalities in the form of oxygen-containing groups were present in a carbon studied using two experimental set-ups. Faradaic peaks, previously not reported in activated carbon were seen. The occurrence of Faradaic phenomena in one experimental set-up but not the other is further analyzed and the origin of these peaks discussed. The particle based mathematical model, where galvanostatic and cyclic voltammetry is simulated, is presented. Concentration profiles both in the particles and electrodes are discussed and some of the numerical results are compared with experimental data. / QC 20100809

In this study, the carbon electrode of supercapacitor was fabricated by using mesocarbon microbeads. For finding the optimal processing parameters of carbon electrode, the effects of specific surface area of activated carbon, the amount of carbon black and binder, and various electrolytes on the capacitative properties of supercapacitor are investigated. To fabricate the composite electrode of supercapacitor, NiO and WO3 thin films were deposited respectively on the carbon electrode by electron beam evaporation. The influences of various scan rates of cyclic voltammograms (CV) on the characteristic of capacitance are studied. The charge-discharge efficiency and life time of the composite electrode are also discussed. Experimental results reveal that the optimum carbon electrode can be obtained using mesocarbon microbeads with high specific surface area (2685 m2/g) and larger pore volume (0.6 cm3/g) and adding 10 wt.% carbon black and 2wt.% binder. The specific capacitances of carbon electrodes in 1 M KOH and 1 M Et4NBF4 are 230.8 F/g and 221.5 F/g, respectively. Besides, the XRD and SEM results showed that NiO and WO3 thin films on composite electrode are sheet-liked crystal structure and stone-liked amorphous structure, respectively. The composite electrode exhibits better capacitance properties than those of carbon electrode at high scan rate by CV analysis. It reveals the promotion of the capacitative property of supercapacitor at higher power density and the improving of the decay property in capacitance at high scan rate. Finally, in the test of charge-discharge efficiency and life time, the charge-discharge efficiency is near 100% after 5000 cycles and it still retains good adhesion between electrode material and substrate.

In recent years, there has been lots of emphasis put on the development of renewable energy. While considerable improvement on renewable energy has been made, there are some inherent limitations for these renewable energies. For example, for solar and wind power, there is an intermittent nature. For the fuel cell, the dynamics of electro-chemical reaction is quite slow compared to the electric load. This will not be acceptable for modern electric application, which requires constant voltage of constant frequency. This work proposed and evaluated a new power circuit that can deal with the problem of the intermittent nature and slow response of the renewable energy. The proposed circuit integrates different renewable energy sources as well as energy storage. By integrating renewable energy sources with statistical tendency to compensate each other, the effect of the intermittent nature can be greatly reduced. This integration will increase the reliability and utilization of the overall system. Moreover, the integration of energy storage solves the problem of the slow response of renewable energy. It can provide the extra energy required by load or absorb the excessive energy provided by the energy sources, greatly improving the dynamics of overall system. To better understand the proposed circuit, "Dual Active Bridge" and "Triple Active Bridge" were reviewed first. The operation principles and the modeling were presented. Analysis and design of the overall system were discussed. Controller design and stability issues were investigated. Furthermore, the function of the central controller was explained. In the end, different simulations were made and discussed. Results from the simulations showed that the proposed multi-port DC-DC power converter had satisfactory performance under different scenarios encountered in practical renewable energy application. The proposed circuit is an effective solution to the problem due to the intermittent nature and slow response of the renewable energy.

Fuel cells are expected to play an important role in future power generation. However, significant technical challenges remain and the commercial breakthrough of fuel cells is hindered by the high price of fuel cell components. As is well known, the fuel cells do not provide the robust source characteristics required to effectively follow the load during significant load steps and they have limited overload-handling capability. Further, the performance of the fuel cell is significantly degraded when the CO (Carbon Monoxide) is contained in the hydrogen fuel. In this thesis several new approaches to improve the performance of PEM based fuel cell power systems are discussed. In the first section an impedance model of the Proton Exchange Membrane Fuel Cell Stack (PEMFCS) is first proposed. This equivalent circuit model of the fuel cell stack is derived by a frequency response analysis (FRA) technique to evaluate the effects of the ripple current generated by the power-conditioning unit. Experimental results are presented to show the effects of the ripple currents. In the second section, a fuel cell powered UPS (Uninterruptible Power Supply) system is proposed. In this approach, two PEM Fuel Cell modules along with suitable DC/DC and DC/AC power electronic converter modules are employed. A Supercapacitor module is also employed to compensate for instantaneous power fluctuations including overload and to overcome the slow dynamics of the fuel processor such as reformers. A complete design example for a 1-kVA system is presented. In the third section, an advanced power converter topology is proposed to significantly improve the CO tolerance on PEM based fuel cell power systems. An additional two-stage dc-dc converter with a supercapacitor module is connected to the fuel cell to draw a low frequency (0.5Hz) pulsating current of the specific amplitude (20-30[A]) from the fuel cell stack. CO on the catalyst surface can be electro-oxidized by using this technique, and thereby the CO tolerance of the system can be significantly improved. Simulation and experimental results show the validity and feasibility of the proposed scheme.