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.

Finite element analysis of electric double layer capacitors using a transient nonlinear Nernst-Planck-Poisson (NPP) model and Nernst-Planck-Poisson-modified Stern layer (NPPMS) model are presented in 1D and 2D. The NPP model provided unrealistic ion concentrations for high electrode surface potential. The NPPMS model uses a modified Stern layer to account for finite ion size, resulting in realistic ion concentrations even at high surface potential. The finite element solution algorithm uses the Newton-Raphson method to solve the nonlinear problem and the alpha family approximation for time integration to solve the NPP and NPPMS models for transient cases. Cubic Hermite elements are used for interfacing the modified Stern and diffuse layers in 1D while serendipity elements are used for the same in 2D. Effects of the surface potential and bulk molarity on the electric potential and ion concentrations are studied. The ability of the models to predict energy storage capacity is investigated and the predicted solutions from the 1D NPP and NPPMS models are compared for various cases. It is observed that NPPMS model provided realistic and correct results for low and high values of surface potential. Furthermore, the 1D NPPMS model is extended into 2D. The pore structure on the electrode surface, the electrode surface area and its geometry are important factors in determining the performance of the electric double layer capacitor. Thus 2D models containing a porous electrode are modeled and analyzed for understanding of the behavior of the electric double layer capacitor. The effect of pore radius and pore depth on the predicted electric potential, ion concentrations, surface charge density, surface energy density, and charging time are discussed using the 2D Nernst-Planck-Poissonmodified Stern layer (NPPMS) model.

<p>Energy storage systems are critically important for many areas in modern society including consumer electronics, transportation and renewable energy production. This dissertation summarizes our efforts on improving the performance metrics of energy storage and conversion devices through rational design and fabrication of hybrid nanomaterial systems. </p><p>This dissertation is divided into five sections. The first section (chapter 2) describes comparison of graphene and carbon nanotubes (CNTs) on improving the specific capacitance of MnO2. We show that CNTs provided better performance when used as ultrathin electrodes but they both show similar performance with rapid MnO2 specific capacitance decrease as electrodes become thicker. We further designed ternary composite electrodes consisting of CNTs, graphene and MnO2 to improve thick electrode performance (chapter 3). We demonstrate that these electrodes were flexible and mechanically strong, had high electrical conductivity and delivered much higher capacity than electrodes made without CNTs. </p><p>Chapter 4 describes assembly of flexible asymmetric supercapacitors using a graphene/MnO2/CNTs flexible film as the positive electrode and an activated carbon/CNTs flexible film as the negative electrode. The devices were assembled using roll-up approach and can operate safely with 2 V in aqueous electrolytes. The major advantage of these devices is that they can deliver much higher energy under high power conditions compared with those designed by previous studies, reaching a specific energy of 24 Wh/kg at a power density of 7.8 kW/kg. </p><p>Chapter 5 describes our approach to improve the energy and power densities of nickel hydroxides for supercapacitors. This was done by assembling CNTs with Co-Ni hydroxides/graphene nanohybrids as freestanding electrodes. The assembled electrodes have dramatically improved performance metrics under practically relevant mass loading densities (~6 mg/cm2), reaching a specific capacitance of 2360 F/g at 0.5 A/g and 2030 F/g even at 20 A/g (~86% retention). </p><p>Finally, we discuss our efforts on designing highly active electrocatalysts based on winged nanotubes for oxygen reduction reactions (ORR). The winged nanotubes were prepared through controlled oxidization and exfoliation of stacked-cup nanotubes. When doped with nitrogen, they exhibited strong activity toward catalyzing ORR through the four-electron pathway with excellent stability and methanol/carbon monoxide tolerance owning to their unique carbon structure.</p> / Dissertation

Darbo tikslas – ištirti superkondensatorių naudą elektros transporto priemonių dinaminėms savybėms. Darbo uždaviniai: apžvelgti akumuliatorių ir superkondensatorių įkrovimo/iškrovimo charakteristikas bei naujausių superkondensatorių technologijas; išanalizuoti kombinuotos baterijų ir superkondensatorių lygiagretaus darbo įkrovimo/iškrovimo sistemą; Apskaičiuoti elektromobilių dinamines charakteristikas naudojant skirtingus ar kombinuotus elektros energijos šaltinius ir palyginant su vidaus degimo varikliu varomo automobilio dinaminėmis charakteristikomis. Buvo nustatyta, kad superkondensatorių panaudojimas tikslingas tik elektromobilyje, kurio maksimalus greitis yra iki 100 km/h. Jei elektromobilio maksimalus greitis didesnis, baterijų atiduodama galia pakankamai didelė įsibėgėti neviršijant baterijų rekomenduojamo srovės stiprio. Vien šiandieniniais superkondensatoriais varomas elektromobilis negali pakeisti automobilio varomo vidaus degimo varikliu, nes maksimalus atstumas, kurį elektromobilis gali nuvažiuoti yra tik 6,3 km. Vien grafeno superkondensatoriais varomo elektromobilio maksimalus greitis prilygsta benzinu varomo automobilio maksimaliam 233,6 km/h greičiui. Toks elektromobilis būtų penkis kartus galingesnis ir nuvažiuotų tokį patį atstumą, kaip vien baterijomis varomas elektromobilis. / The main objective of the work is to explore the benefits of supercapacitor for electric vehicle dynamic characteristics. The goal of work: to overview the battery and supercapacitor charge / discharge characteristics and the latest technologies of supercapacitors, to analyze the combination of batteries and supercapacitors in “Buck – Boost” converter, Calculate electric dynamic characteristics using different or combined electric energy sources, and compare to an internal combustion engine driven vehicle dynamic characteristics. It was found that the supercapacitor is purposive only electric vehicle, with a maximum speed of 100 km / h. If the top speed of electric car is over 100 km/h then a total power output of batteries is large enough to accelerate and not to exceed the recommended current of the battery. Electric vehicle powered today’s supercapacitors can not replace the internal combustion engine because the maximum distance you can travel is only 6.3 km. graphene supercapacitors driven electric vehicle maximum speed is equivalent gasoline-powered car for a maximum of 233.6 km / h. This electric car is five times more powerful and driven the same distance as the battery-powered electric vehicle.

As a result of increasing demand of power in the modern society, energy storage/consumption is playing a more important role on future economics. Therefore energy storage systems which are more environmentally friendly, low-cost and high-performance have attracted much attention. Among electrochemical systems, supercapacitors are considered as a prominent candidate for the modern energy storage systems due to the high power density, high charge/discharge rate, and long lifetimes. Nevertheless, the performance of supercapacitors is limited by the significant disadvantage of low energy density. Metal oxides with high pseudocapacitance such as MnO2 are used as the electrode materials for supercapacitors to resolve the lack of energy density in supercapacitors. The specific capacitance is notably enhanced by the metal oxides because of the reversible redox reactions. Previous studies confirmed that only a thin layer of MnO2 is involved in the redox process and is electrochemically active, which makes surface area a critical factor of energy storage. To increase surface area of MnO2, ZnO nanostructure is introduced in the electrode material as a template for electrodeposition of MnO2. In the first part of the research, we synthesize a nanomaterial which combines 0-1-2 dimensional properties of different nanostructures and significantly increases the energy capacity of MnO2. iv In the second part of the research, we demonstrate an in situ synthesis of a hybrid device that combines two materials to investigate the individual characteristic of two nanomaterials. In this study, a ZnO nanorod interface on Au nanoparticle arrays is fabricated, and results in the photo-modulation of the array characteristics. We find the use of nanoparticle arrays as electrochemical systems by electrodepositing ZnO on Au nanoparticle arrays. The method expands their potential use in sensors, multifunctional materials, single electron transistors and nanoscale energy systems. Characteristic behavior of Au nanoparticle arrays including Coulomb blockade at room temperature, single electron charging effects and a power law dependence in current-voltage were observed, and Schottky behavior and photocurrent generation due to the ZnO nanorods were also proved. From the modulation of the threshold voltage of the Au array due to the electron-hole pairs generated by photo excitation in the ZnO rods, it can be seen that the system also has coupling between the Au nanoparticles and ZnO rods other than the individual characteristics. Au nanoparticles can be used as electrochemical systems with both structural and spatial confinement of the synthesized material. The possibility of using Au nanoparticle chains as electroactive sites significantly expands their potential use in sensors, multifunctional materials, single electron transistors and nanoscale energy systems.

The supercapacitor is one of the most important energy storage devices as its construction allows for addressing many of the drawbacks related to batteries, but the low energy density of current systems is a major issue. In this doctoral dissertation, with a view to attaining high energy density supercapacitor systems that can be comparable to those for batteries, new heteroatom-containing carbons in the form of particles and three-dimensional films were investigated. A nitrogen-containing material, acrodam, was chosen as the carbon precursor due to the inexpensiveness, high carbonization yield, oligomerizability, etc. The carbon particles were prepared from acrodam together with caesium acetate as a meltable flux agent, and disclosed excellent properties in hydroquinone-loaded sulphuric acid electrolyte with high energy densities (up to 133.0 Wh kg–1) and sufficient cycle stabilities. These properties are already now comparable to those of batteries. Besides, conductive carbon three-dimensional films were fabricated using acrodam oligomer as the precursor by the inexpensive spin coating method. The films were found to be homogeneous, flat, void- and crack-free, and high conductivities (up to 334 S cm–1) could be obtained at the carbonization temperature of 1000 ºC. Furthermore, a porous carbon three-dimensional film could be formed using an organic template at the first attempt. This finding demonstrates the film’s potentiality for various applications such as supercapacitor electrode; the essential absence of contact resistance within the network should contribute to effective transportation of electron within the electrode. The progress made in this dissertation will open a new way to further enhancement of energy density for supercapacitor as well as other applications that exceeds the current properties. / Der Superkondensator ist einer der wichtigsten Energiespeicher da seine Konstruktion die Lösung vieler Nachteile von Batterien erlaubt. Allerdings weisen derzeitige Systeme noch zu geringe Energiedichten auf. Um Superkondensatoren mit Energiedichten vergleichbar zu Batterien zu ermöglichen, wurden in der vorliegenden Dissertation neue, heteroatomhaltige Kohlenstoffe in Form von Partikeln und Filmen untersucht. Aufgrund geringer Kosten, hohen Ausbeuten, Polymerisierbarkeit usw. wurde die stickstoffhaltige Substanz Acrodam als Kohlenstoffvorstufe verwendet. Die Kohlenstoffpartikel wurden ausgehend von Acrodam zusammen mit Cäsiumacetat als schmelzbares Flussmittel hergestellt und wiesen ausgezeichnete Eigenschaften in Hydrochinon geladenen Schwefelsäure-Elektrolyten mit hohen Energiedichten (bis zu 133,0 Wh kg–1) und guten Zyklusstabilitäten auf. Diese Eigenschaften sind bereits jetzt vergleichbar mit denen von Batterien. Weiterhin wurden unter Verwendung von Acrodamoligomeren als Vorstufe und mit Hilfe der kostengünstigen Rotationsbeschichtung leitfähige, dreidimensionale Kohlenstofffilme hergestellt. Bei einer Karbonisierungstemperatur von 1000 °C konnten die Materialien als homogene, flache, Hohlraum-und Riss-freie Filme erhalten werden, die eine hohe Leitfähigkeit (bis zu 334 S cm–1) aufwiesen. Darüber hinaus konnte mit einem organischen Templat ein dreidimensionaler, poröser Kohlenstoff geformt werden. Dies zeigt das Potential der Filme für verschiedene Anwendungen wie Superkondensatorelektroden; die Abwesenheit von Übergangswiderständen im Netzwerk sollte zu einem effizienten Transport von Elektronen in der Elektrode beitragen. Die Ergebnisse dieser Dissertation werden neue Wege zur Verbesserung der Energiedichte von Superkondensatoren sowie weiteren Anwendungen eröffnen.

High mobility has been a standard in the modern world for decades. This has resulted in high energy consumption, diminishing fossil energy reserves and rising levels of greenhouse gases. By recovering the energy lost in deceleration of vehicles the total energy consumption can be decreased and exhaust emissions reduced. This can be done with a kinetic energy recovery system (KERS) that converts kinetic energy to electric energy during deceleration, which then can be used for acceleration. KERS requires an electrical storage device with high power density, due to the high power levels generated at heavy braking. Batteries does not generally meet these requirements, especially in the cost-effective point of view, but different types of capacitors can be used to obtain a cheap and effective system. To get such an energy storage device small, lightweight and inexpensive while the technology is sustainable requires avoidance of rare metals and hazardous materials. In this master thesis energy and power levels for KERS has been modelled, based on standardized measurements techniques and small paper-based supercapacitors have been built and tested in order to model size, weight and price for a full-scale energy storage device to a KERS-application. The models showed that energy consumption in urban traffic could be reduced with 18% and with an electrode material for the energy storage device with a capacitance of about 1500 F/m2 a reasonable size and weight is obtained. To reach these values of capacitance in paper-based supercapacitors further testing is required on area and layer dependence and for different electrodes.

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.

In this research, manganese oxide based nanoparticles were synthesized by sol-gel process. Methanol, ethanol, and propanol were used as alternative solvents during sol-gel process with manganese acetate as precursor for the preparation of pristine manganese oxide. Hybrid manganese oxide modified by additions of carbon nanotubes was further prepared. The effects of different solutions and heat treatment temperatures on the morphology, physical characteristics, and electrochemical properties of the manganese oxide based materials were investigated. Particle size of pristine manganese oxide samples prepared from methanol, ethanol, and propanol were compared by SEM and TEM image analysis. Smallest particle size was observed for manganese oxide prepared from propanol, with diameters range from 16 nm to 50nm. XRD results showed that the as-prepared manganese oxide based samples treated at calcination temperature of 300ºC and above were composed of Mn2O3 as dominant phase, with Mn3O4 as minor phase. Specific capacitance of manganese oxide prepared from methanol, ethanol, and propanol at scan rate of 10 mV/s measured using two electrode systems were 88.3, 66.0, and 104.8 F/g, respectively and that for the hybrid sample was 140.5 F/g. Results from electrochemical impedance spectroscopy (EIS) also showed superior electrochemical properties of the hybrid sample over pristine manganese oxide samples. It is evident that the addition of carbon nanotubes not only improved the specific capacitance but also the overall electrochemical properties of the manganese oxide supercapacitor.

Master of Science / Department of Mechanical and Nuclear Engineering / Gurpreet Singh / Polymer-derived ceramics (PDCs) such as silicon oxycarbide (SiOC) have shown promise as an electrode material for rechargeable Li-ion batteries (LIBs) owing to the synergy between its disordered carbon phase and hybrid bonds of silicon with oxygen and carbon. In addition to their unique structure, PDCs are known for their high surface area (~822.7 m² g⁻¹), which makes them potential candidates for supercapacitor applications. However, low electrical conductivity, voltage hysteresis, and first cycle lithium irreversibility have hindered their introduction into commercial devices. One approach to improving charge storage capacity is by interfacing the preceramic polymer with boron or aluminium prior pyrolysis. Recent research has shown that chemical interfacing with elemental boron, bulk boron powders and even exfoliated sheets of boron nitride leads to enhancements in thermal and electronic properties of the ceramic. This thesis reports the synthesis of a new type of PDC composite comprising of SiOC embedded with boron nitride nanotubes (BNNTs). This was achieved through the introduction of BNNT in SiOC pre-ceramic polymer at varying wt.% loading (0.25, 0.5 and 2.0 wt.%) followed by thermolysis at high temperature. Electron microscopy and a range of spectroscopy techniques were employed to confirm the polymer-to-ceramic transformation and presence of disordered carbon phase. Transmission electron microscopy confirmed the tubular morphology of BNNT in the composite. To test the material for electrochemical applications, the powders were then made into free-standing paper-like electrodes with reduced graphene oxide (rGO) acting as support material. The synthesized free-standing electrodes were characterized and tested as electrochemical energy storage materials for LIBs and symmetric supercapacitor applications. Among the SiOC-BNNT composite paper tested as anode materials for LIBs, the 0.25 wt.% BNNT composite paper demonstrated the highest first cycle lithiation capacity corresponding to 812 mAh g⁻¹ (at a current density of 100 mA g⁻¹) with a stable charge capacity of 238 mAh g⁻¹ when asymmetrically cycled after 25 cycles. On the contrary, the 0.5 wt.% BNNT composite paper demonstrated the highest specific capacitance corresponding to 78.93 F g⁻¹ at a current density of 1 A g⁻¹ and a cyclic retention of 86% after 185 cycles. This study shows that the free carbon content of SiOC-BNNT ceramic composite can be rationally modified by varying the wt.% of BNNT. As such, the paper composite can be used as an electrode material for electrochemical energy storage.