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<p>The development of all-electric or plug-in hybrid vehicles requires the use of advanced energy storage devices with high power. Dedicated for energy storage, electrochemical supercapacitors (ES) offer the advantage of high power density. High power ES can provide load-leveling for batteries and fuel cells during starting, acceleration, hill climbing and braking. ES are important for reducing cycling of batteries, thus extending their lifetime by energy storage and delivery during fast transient operations such as in braking (storage) or start up and acceleration (supply).</p> <p>The interest in polypyrrole (PPY) for the application in ES is attributed to the high specific capacitance (SC) of this material. The possibility of PPY deposition on stainless steel substrates is important for the practical applications of PPY films in ES, using low cost stainless steel current collectors. The important task is to avoid anodic dissolution of the substrates during PPY electropolymerization. Polypyrrole (PPY) films were electrochemically deposited on stainless steel substrates or Ni plaque from aqueous pyrrole solutions containing anionic additives. The method resulted in the formation of adherent and uniform films. The deposition yield was investigated at galvanostatic conditions. It was found that anionic additives can be used for the dispersion of multiwall carbon nanotubes (MWCNTs) and fabrication of composite PPY–MWCNT films. The deposition yield was studied under galvanostatic conditions. The mechanism of PPY–MWCNTs deposition was discussed. The incorporation of MWCNTs into the PPY during electropolymerization resulted in the formation of porous films. The films were investigated for the application in electrodes of electrochemical supercapacitors. Electrochemical testing in the 0.5M Na₂SO₄ electrolyte solutions showed a capacitive behaviour in a voltage window of -0.5 to +0.4 V versus a saturated calomel electrode. The results indicated that the PPY–MWCNT films deposited on the stainless steel and nickel plaque substrates are promising electrode materials for ES.</p> / Master of Applied Science (MASc)

<p>No comments. Thanks.</p> / <p>Advanced electrodes based on MnO₂ for the electrochemical supercapacitor (ES) application have been fabricated using electrochemical and chemical methods.</p> <p>Electrosynthesis method has been utilized for the in-situ impregnation of manganese dioxide in commercial Ni plaque current collectors. Dipping-reduction, cathodic galvanostatic and reverse pulse electrosynthesis methods were investigated. The material loading was varied by the variation of the number of the dipping-reduction procedures in the chemical precipitation method or by the variation of charge passed in the electrochemical methods. The results obtained by different methods were compared. The dipping-reduction method offered the advantage of higher specific capacitances (SCs) at high scan rates, whereas other methods allowed higher material synthesis rate.</p> <p>Cathodic electrolytic deposition (ELD) has been utilized for the fabrication of Ag-doped MnO₂ films. The Ag-doped MnO₂ films showed improved capacitive behavior and lower electrical resistance of 0.6 Ohm compared to pure MnO₂ films. The highest SC of 770 F g^-1 was obtained at a scan rate of 2 mV s^-1 in the 0.5 M Na₂SO₄ electrolyte.</p> <p>Electrodes for ES application were fabricated by cathodic electrodeposition of MnO₂ on CNTs, which were grown by chemical vapor deposition on stainless steel meshes. The MnO₂-CNT nanocomposites showed excellent capacitive behavior and low electrical resistance of 0.5 Ohm.</p> <p>Electrophoretic deposition (EPD) has been utilized for the deposition of composite MnO₂-multiwalled carbon nanotube (MWCNT) films for the ES application. Dopamine (DA), caffeic acid (CA), tyramine (TA), gallic acid (GA), polyacrylic acid (PAA) and pyrocatechol violet (PV) were shown to be effective and universal charging additives, which provide stabilization of MnO₂ nanoparticles and MWCNTs in the suspensions. The influence of the structure of the organic molecules on their adsorption on the oxide nanoparticles has been investigated. We discovered that the number and site of OH group for dispersants were essential for the adsorption on oxide materials, and the number of aromatic ring was important for the adsorption on carbon materials. Pure CNT films were deposited using PV as a dispersant, which was the first time in literature to prepare pure CNT film using a dispersant. SCs decrease with increasing film thickness. SCs of composite MnO₂-MWCNT obtained using EPD were in the range of 350-650 F g^-1 depending on material loadings.</p> / Doctor of Science (PhD)

The superior properties of carbon nanotubes (CNTs) are best manifest in bulk materials when the CNTs are organized in tandem and embedded in a continuous matrix. Decorating the CNTs with magnetic nanoparticles (MNPs) facilitates their expedient organization with a magnetic field. One of the most convenient methods for their decoration is to first treat the CNTs with oxidative acids, and then coprecipitated MNPs in situ. This method results magnetized CNTs that are covalently functionalized with the MNPs. The associated destruction in the CNTs required running a comparative study of this protocol to identify the influence of the acid treatment on the decoration of multiwalled CNTs (MWNTs). Further, we explore means to tune the physical properties of these magnetized CNTs (mMWNTs) by varying the (1) MNP material composition, and (2) MNP:MWNT (w/w) magnetization weight ratio (γ). The resulted composite materials (mMWNTs) are utilized to synthesize a novel and hitherto unreported class of colloidal suspensions (MCCs) for which the dispersed phase, which consists of MWNTs decorated with MNPs, is both magnetoresponsive and electrically conductive. Synthesis of the dispersed phase merges processes for producing ferrofluids and mMWNTs. Later, these MCCs are adapted and engineered to produce a biological ink containing MWNTs that are twice functionalized, first with MNPs and thereafter with the anti-c-Myc monoclonal antibodies (Abs). The ink is pipetted and dynamically self-organized by an external magnetic field into a dense electrically conducting sensor strip that measures the decrease in current when a sample containing c-Myc antigens (Ags) is deposited on it. On the other side, a nondestructive methods to magnetize MWNTs and provide a means to remotely manipulate them is through the electroless deposition of magnetic nickel nanoparticles on their surfaces. The noncovalent bonds between Ni nanoparticles and MWNTs produce a Ni-MWNT hybrid material (NiCH) that is electrically conductive and has an enhanced magnetic susceptibility and elastic modulus. Raising γ (Ni:MWNT weight ratios) increases the coating layer thickness, which influences the NiCH magnetic properties and tunes its elastic modulus. The NiCH was used to fabricate Ni-MWNT macrostructures and tune their morphologies by changing the direction of an applied magnetic field. Leveraging the hydrophilic Ni-MWNT outer surface, a water-based conductive ink was created and used to print a conductive path that had an electrical resistivity of 5.9 Ωm, illustrating the potential of this material for printing electronic circuits. Further, the NiCHs are introduced into an epoxy matrix at low 0.25-1% volume fractions and aligned along the direction of an applied magnetic field, which produces anisotropic bulk properties. However, nanoparticles aligned in perpendicular directions in sequential layers result in an effectively isotropic composite material. Furthermore, the subsequent annealing of the NiCH in the presence of air oxidizes nickel to nickel oxide whereas carbon is released as gaseous carbon dioxide, which leads to a novel approach for the fabrication of nickel oxide nanotubes (NiONTs) based on MWNTs as a sacrificial template. New chelating polyelectrolytes are used as dispersing agents to achieve high colloidal stability both for NiCH and NiONTs. A gravimetric specific capacitance of 245.3 F g-1 and areal capacitance of 3.28 F cm-2 at a scan rate of 2 mV s-1 is achieved with an electrode fabricated using nickel oxide nanotubes as the active element with a mass loading of 24.1 mg/cm2. / Thesis / Doctor of Philosophy (PhD) / The superior properties of carbon nanotubes (CNTs) are best manifested in bulk materials when the CNTs are organized axially and in tandem, and embedded in a continuous matrix. Decorating the CNTs with magnetic nanoparticles (MNPs) facilitates their organization through “action from a distance” with a magnetic field. The attachment of MNPs to the surfaces of CNTs can be realized through covalent or non-covalent (i.e. physical) bonding. This work develops both methodologies to investigate how the physical properties of magnetized CNT (mCNT) can be tuned and produce new CNT-based nanostructures for particular applications. First, mCNTs are utilized to synthesize a hitherto unreported class of colloidal suspensions based on which a magnetic bio-ink is fabricated to print a fast-response biological sensor. Next, nickel-coated CNTs prepared using electroless deposition are used in the form of a filler at low volume fractions in an epoxy matrix, where they are aligned along multiple-direction using a magnetic field, producing either anisotropic or isotropic bulk properties on demand. Finally, subsequent annealing of nickel-coated CNTs in air oxidizes nickel to nickel oxide while carbon is released in the form of gaseous carbon dioxide. This leads to another novel approach for the fabrication of nickel oxide nanotubes, which are demonstrated to be an alternate viable material to fabricate electrodes for use in supercapacitors.

The research performed aims to develop a deeper understanding and prediction of behaviour of complex chemical and physical systems using density functional theory (DFT) modelling complemented by experimental techniques. We focus on phenomena relevant to practical applications of semiconducting materials. Semiconductor nanowires, produced by the vapor-liquid-solid method are being considered for applications in photo sensors, field effect transistors, light emitting diodes (LEDs) and energy harvesting devices. In particular, semiconductor nanowire based photovoltaic devices show potential for lower cost due to less material utilization and greater energy conversion efficiency arising from enhanced photovoltage or photocurrent due to hot carrier or multiexciton phenomena enhanced light absorption, compared to conventional thin film devices. Further, freedom from lattice matching requirements due to strain accommodation at the nanowire surfaces enable compatibility with a wide variety of substrates including Silicon. Thus understanding and improving the optoelectronic properties of nanowires is of great interest. In the first paper, we study the effect of planar defects on optoelectronic properties of nanowire based semiconductor devices. Specifically, we were interested in investing the origin of various features observed in the photoluminisence (PL) spectrum of GaP nanowire using density functional modelling, which are not well understood. In the second paper, we work to model bonding characteristics during a chemical synthesis. We focus on the synthesis of nanoparticles for supercapacitor application. In the past decade, comprehensive research has been emphasized on manganese oxides for electrochemical supercapacitor (ECS) applications. Mn3O4 has gained significant interest due to its compatibility with capping agents and the unique spinel structure allows for potential modifications with other cations. Many metal oxide synthesis techniques are based on aqueous processing. The synthesized particles are usually dried and redispersed in organic solvents to incorporate water-insoluble additives such as binders to fabricate films and devices. However, during the drying step nano-structures are highly susceptible to agglomeration, which can be attributed to the condensation reactions occurring between particles and reduction in surface energy. Poor electrolyte access due to agglomeration and low intrinsic conductivity of Mn3O4 are detrimental to the performance of Mn 3O4 electrode especially at high active mass loadings. Numerous attempts have focused on controlling size and morphology of Mn3O4 nanostructures using capping agents, which have strong adhesion to particles surface to inhibit agglomeration. Catechol containing molecules have been used for dispersion of metallic nanoparticles and fabrication of composite thin films, resulted in narrow size distribution of nanoparticles and strong adhesion to substrates. Despite the experimental results showing good adsorption of catechol group to metal atoms, the mechanism is unclear since it is highly influenced by synthesis parameters. We use Infrared spectroscopy in conjugation with density functional modelling to understand the binding mechanism of 3,4 dihydroxy benzaldehyde onto Mn3O4 surface. / Thesis / Master of Applied Science (MASc)

Control and monitoring networks often operate on AC/DC power systems. DC batteries and chargers are commonly used on industrial plants as auxiliary DC power systems for these control and monitoring networks. The energy demand and load profiles for these control networks differ from application to application. Proper design, sizing, and maintenance of the components that forms part of the DC control power system are therefore required. Throughout the load profile of a control and monitoring system there are various peak currents. The peak currents are classified as inrush and momentary loads. These inrush and momentary loads play a large role when calculating the required battery size for an application. This study investigates the feasibility of using supercapacitors in conjunction with batteries, in order to reduce the size of the required battery capacity. A reduction in the size of the required battery capacity not only influences the cost of the battery itself, but also influences the hydrogen emissions, the physical space requirements, and the required rectifiers and chargers. When calculating the required size batteries for an auxiliary power system, a defined load profile is required. Control and monitoring systems are used to control dynamic processes, which entails a continuous starting and stopping of equipment as the process demands. This starting and stopping of devices will cause fluctuations in the load profile. Ideally, data should be obtained from a live plant for the purpose of defining load profiles. Unfortunately, due to the economic risks involved, installing data logging equipment on a live industrial plant for the purpose of research, is not allowed. There are also no historical data available from which load profiles could be generated. In order to evaluate the influence of supercapacitors, complex load profiles are required. In this study, an alternative method of defining the load profile for a dynamic process is investigated. Load profiles for various applications are approximated using a probabilistic approach. The approximation methodology make use of plant operating philosophies as input to the Markov Chain Monte Carlo simulation theory. The required battery sizes for the approximated profiles are calculated using the IEEE recommended practice for sizing batteries. The approximated load profile, as well the calculated battery size are used for simulating the auxiliary power system. A supercapacitor is introduced into the circuit and the simulations are repeated. The introduction of the supercapacitor relieves the battery of the inrush and momentary loads of the load profile. The battery sizing calculations are repeated so as to test the influence of the supercapacitor on the required battery capacity. In order to investigate the full influence of adding a supercapacitor to the design, the impact on various factors are considered. In this study, these factors include the battery size, charger size, H2 extraction system, as well as maintenance requirements and the life of the battery. No major cost savings where evident from the results obtained. Primary reasons for this low cost saving are the fixed ranges in which battery sizes are available, as well as conservative battery data obtained from battery suppliers. It is believed that applications other than control and monitoring systems will show larger savings. / MIng (Computer and Electronic Engineering), North-West University, Potchefstroom Campus, 2015

Control and monitoring networks often operate on AC/DC power systems. DC batteries and chargers are commonly used on industrial plants as auxiliary DC power systems for these control and monitoring networks. The energy demand and load profiles for these control networks differ from application to application. Proper design, sizing, and maintenance of the components that forms part of the DC control power system are therefore required. Throughout the load profile of a control and monitoring system there are various peak currents. The peak currents are classified as inrush and momentary loads. These inrush and momentary loads play a large role when calculating the required battery size for an application. This study investigates the feasibility of using supercapacitors in conjunction with batteries, in order to reduce the size of the required battery capacity. A reduction in the size of the required battery capacity not only influences the cost of the battery itself, but also influences the hydrogen emissions, the physical space requirements, and the required rectifiers and chargers. When calculating the required size batteries for an auxiliary power system, a defined load profile is required. Control and monitoring systems are used to control dynamic processes, which entails a continuous starting and stopping of equipment as the process demands. This starting and stopping of devices will cause fluctuations in the load profile. Ideally, data should be obtained from a live plant for the purpose of defining load profiles. Unfortunately, due to the economic risks involved, installing data logging equipment on a live industrial plant for the purpose of research, is not allowed. There are also no historical data available from which load profiles could be generated. In order to evaluate the influence of supercapacitors, complex load profiles are required. In this study, an alternative method of defining the load profile for a dynamic process is investigated. Load profiles for various applications are approximated using a probabilistic approach. The approximation methodology make use of plant operating philosophies as input to the Markov Chain Monte Carlo simulation theory. The required battery sizes for the approximated profiles are calculated using the IEEE recommended practice for sizing batteries. The approximated load profile, as well the calculated battery size are used for simulating the auxiliary power system. A supercapacitor is introduced into the circuit and the simulations are repeated. The introduction of the supercapacitor relieves the battery of the inrush and momentary loads of the load profile. The battery sizing calculations are repeated so as to test the influence of the supercapacitor on the required battery capacity. In order to investigate the full influence of adding a supercapacitor to the design, the impact on various factors are considered. In this study, these factors include the battery size, charger size, H2 extraction system, as well as maintenance requirements and the life of the battery. No major cost savings where evident from the results obtained. Primary reasons for this low cost saving are the fixed ranges in which battery sizes are available, as well as conservative battery data obtained from battery suppliers. It is believed that applications other than control and monitoring systems will show larger savings. / MIng (Computer and Electronic Engineering), North-West University, Potchefstroom Campus, 2015

Les piles à combustible sont des convertisseurs électrochimiques. Elles convertissent l’énergie chimique en une énergie électrique directement disponible grâce à une réaction d’oxydoréduction. Dans notre cas, nous nous intéressons aux piles à membrane protonique plus communément appelées PEMFC (Proton Exchange Membrane Fuel Cell) qui fonctionne à l’hydrogène. Ce type de pile domine le marché puisqu’elles conviennent à de nombreuses applications portables et stationnaires. Si l’on s’intéresse aux PAC pour des utilisations stationnaires, des durées de vie supérieures à 10 000 h peuvent être atteintes. Cependant, celles-ci se réduisent significativement pour des applications de type transport avec de fréquents arrêts et démarrages ainsi que d’importantes variations de puissance : dans ce cas, 3000 h de fonctionnement semblent constituer une limite difficile à dépasser. En régime instationnaire, les fluctuations de puissance impactent les conditions opératoires de la pile et génèrent des phénomènes locaux accélérant son vieillissement. L’intérêt de l’hybridation est d’élargir le champ d’application des systèmes pile à combustible en les rendant capables de répondre aux exigences des applications de type transport. Dans notre cas, il s’agit d’une structure parallèle, avec comme source d’énergie principale, une pile à combustible assistée d’un moyen de stockage, les supercapacités. A travers nos travaux, nous avons recherché à déterminer les avantages que peut offrir l’hybridation en termes de simplification de système : identifier les composants ou sous-systèmes qui limitent la dynamique de la pile à combustible, comprendre les mécanismes mis en jeu et étudier les solutions que peut offrir l’association des SC à la PAC. L’ajout de supercapacités, en tant que sources secondaires, permet d’obtenir une densité de puissance plus élevée et ainsi d’adapter le système PAC à des applications instationnaires. Nous avons également observé qu’il est possible de concevoir des systèmes fiables en limitant le vieillissement des piles. Les travaux ont permis de tester des supercapacités planes élaborées par l’IMN. L’intérêt est de pouvoir produire des supercapacités planes performantes à bas coût et non néfaste pour l’environnement / Fuel cell are an electrochemical devices wich convert chemical energy into electricity. In this study we focus on PEMFC Proton Exchange Membrane Fuel Cells fede by hydrogen and air. This kind of fuel cell has many advantages and show extensive application potentials. If PEMFC exhibits good power capability during steady-state operation, the slow response during transient peak power demands has restrained them for being used in large-scale and high-power transportation applications, such as automobive. To overcome these difficulties, a variety of research has been carried out on the development of hybrid systems based on supercapacitors or batteries. In this work, we study the effect of passive hybridization to improve the system performance and reliability, more specifically during steep load variations. We show that SC can provide a sufficient amount of power to the system during the short time needed by the gas supply lines to respond to an increase in power or current density. This makes it possible to always feed the fuel cell with the right amount of gas without anticipating current peaks or load variations. Flat supercapacitors were also designed and made within the framework of this project. The aim was to design cheap and safe SC with materials like activated carbon electrode and LiNO3 as the electrolyte. In this study we also showed how a direct passive hybridization of PEMFC with small aqueous supercapacitors brings to the design of more efficient, simple and reliable FC systems. By using transient load (Heaviside steps), we showed that the direct hybridization of PEMFC with SC allows to extend its lifetime

L‟acétonitrile (ACN) peut être considéré comme le solvant de référence utilisé dans les électrolytes pour supercondensateurs car, industriellement, il est le plus utilisé. Il présente en effet de nombreux avantages tels qu‟une viscosité faible et une permittivité élevée, conduisant à une excellente conductivité en présence d‟un sel. Il est cependant hautement volatile, très inflammable et toxique quand il brûle (dégagement de HCN). Ainsi, dans le but de réduire sa pression de vapeur, et donc le risque d‟inflammabilité, il peut être mélangé à un liquide ionique (LI) qui lui est non volatile. Le but de ce travail est de remplacer l‟électrolyte classique des supercondensateurs à base de ACN et de sel de tétraethylammonium tétrafluoroborate (ACN + 1M Et4N+BF4-) par un mélange LI/ACN. Pour ce faire, l‟étude physico-chimique, électrochimique et thermodynamique des mélanges LI/ACN est entreprise. Dans un premier temps, les liquides ioniques ont été synthétisés et caractérisés par différentes techniques d‟analyses physico-chimiques. Ensuite des mélanges LI/ACN ont été formulés. Ces mélanges ont subi des tests de sécurité (tests préliminaires d‟inflammabilité, mesures de point flash) afin de trouver le mélange optimal. Les phénomènes de transport dans ces mélanges ont été aussi étudiés afin de comprendre leur comportement en température. Par ailleurs, l‟étude électrochimique menée sur ces mélanges a montré qu‟il n‟y avait pas de dégradation des performances électrochimiques par comparaison à l‟électrolyte classique. Enfin l‟étude de l‟équilibre liquide vapeur à partir de modèles thermodynamiques semi-prédictifs comme UNIQUAC ou prédictifs comme Cosmo-RS a permis de déterminer les grandeurs d‟excès. / Acetonitrile (ACN) is the most popular solvent in electrolytes designed for use in supercapacitors. It presents many advantages such as a low viscosity and a high permittivity, leading to excellent conductivities in the presence of salts. However it is highly flammable and very toxic when burning (release of HCN ). Thus, in order to reduce its vapor pressure and hence its flammability we propose to mix it with an ionic liquid (IL). As ILs are non volatile compounds, the vapor pressure of the mixture will be reduced (Raoult‟s law). In addition many other benefits may be expected from these mixtures. The aim of this work is to replace the conventional ACN and Et4NBF4 based electrolyte for supercapacitors by a IL/ACN mixture. Thus, the physico-chemical, electrochemical and thermodynamical studies of IL/ACN mixtures have been undertaken. Synthesized and commercial ILs are characterized by mean of different physico-chemical analysis. Then IL/ACN mixtures were formulated. These mixtures were tested for safety (preliminary flammability tests, flash point measurements) and the optimal mixture determined. Transport phenomena in these mixtures were also studied to understand their behavior in response to temperature. Furthermore, the electrochemical study conducted on these mixtures showed that there was no degradation of the electrochemical performances as compared to the conventional electrolyte. Finally the study of vapor liquid equilibrium from semi-predictive thermodynamic models like UNIQUAC or predictive models like Cosmo-RS allowed us to determine the excess properties.

<p>U disertaciji je opisan namenski projektovan bežični senzorski čvor namenjen za praćenje parametara životne sredine. Razvijeno rešenje se odlikuje malom cenom i dimenzijama, širokom primenom i minimalnim utocajem na životnu sredinu u poređenju sa primerima iz literature. Koristi se prikupljanje energije sunca iz okoline i superkondenzator za napajanje, što utiče na povećanje životnog veka i smanjivanje troškova održavanja. Izvršena testiranja su potvrdila funkcionalnost predloženog rešenja i mogućnost praćenja različitih parametara korišćenjem komercijalnih i namenski projektovanih senzora. Unapređeno, modularno, rešenje rešava uočena ograničenja i povećava broj parametara životne sredine koji se mogu pratiti.</p> / <p>The dissertation describes a specially designed WSN node for application in<br />environmental monitoring. The developed solution is characterized by low price and<br />dimensions, wide application and minimal environmental impact compared to<br />example in literature. Solar energy harvesting and supercapacitor are used as power<br />supply, which increase node lifetime and reduce maintenance costs. The performed<br />tests confirmed the functionality of the proposed solution and the ability to monitor<br />various environmental parameters using commercial and specially designed sensors.<br />The new enhanced solution, with modular design, solves the observed limitations and<br />increases the number of environment parameters that can be monitored.</p>