Thesis advisor: Dunwei Wang / In this work, we present our findings regarding the low-temperature, solid-state conversion of Cu₂S nanowires to Cu₂S/Cu₅FeS₄ rod-in-tube structures, Cu₂S/ZnS segmented nanowires, and a full conversion of Cu₂S nanowires to ZnS nanowires. These conversion reactions occur at temperatures as low as 105 degrees Celsius, a much lower temperature than those required for reported solid-state reactions. The key feature of the Cu₂S nanowires that enables such low conversion temperatures is the high ionic diffusivity of the Cu⁺ within a stable S sublattice. The second portion of this work will focus on the oxide-stabilization and utilization of TiSi₂ nanonets as a lithium-ion battery anode. This nanostructure, first synthesized in our lab, was previously demonstrated to possess a lithium storage capacity when cycled against a metallic Li electrode. However, with subsequent lithiation and delithiation cycles, the TiSi₂ nanonet structure was found to be unstable. By allowing a thin oxide layer to form on the surface of the nanonet, we were able to improve the capacity retention of the nanonets in a lithium-ion half-cell; 89.8% of the capacity of the oxide-coated TiSi₂ was retained after 300 cycles compared to 62.3% of the capacity of as-synthesized TiSi₂ nanonets after 300 cycles. The layered structure of C49 TiSi₂ exhibited in the nanonets allows for a specific capacity greater than 700 mAh g(-1), and the high electrical conductivity of the material in conjunction with the layered structure confer the ability to cycle the anode at rates of up to 6C, i.e., 10 minute charge and discharge cycles, while still maintaining more than 75% of the capacity at 1C, i.e., 1 hour charge and discharge cycles. / Thesis (MS) — Boston College, 2013. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

A four quadrant general single-phase bi-directional DC/DC converter was designed and constructed for high effect systems. The target application for the DC/DC converter was to be used to transfer energy between different energy storages, a miniature DC power grid and the high voltage AC power city grid. The converter is capable of step-up and step-down operations in both directions i.e. it is bi-directional at varying voltage levels. Different DC/DC topologies were investigated, and thereafter simulations were performed in LTspice and Simulink to ensure its capabilities and functionalities. The result of the simulations was a two layered PI-regulator, controlling both the external DC-grid voltage and inductor current through the converter. Once a suitable topology and control strategy was found, a suitable power transistor investigated and a PCB driver card were developed with KiCad. The final converter is capable to seamlessly change between its four modes and controlling voltages up to 1200 V and currents up to 200 A.

Solar energy has the potential to meet all of society’s energy demands, but challenges remain in storing it for times when the sun is not shining. Electrolysis is a promising means of energy storage which applies solar-derived electricity to drive the production of chemical fuels. These so-called solar fuels, such as hydrogen gas produced from water electrolysis, can be fed back to the grid for electricity generation or used directly as a fuel in the transportation sector. Solar fuels can be generated by coupling a photovoltaic (PV) cell to an electrolyzer, or by directly converting light to chemical energy using a photoelectrochemical cell (PEC). Presently, both PV-electrolyzers and PECs have prohibitively high capital costs which prevent them from generating hydrogen at competitive prices. This dissertation explores the design of membraneless electrolyzers and PECs in order to simplify their design and decrease their overall capital costs. A membraneless water electrolyzer can operate with as few as three components: A cathode for the hydrogen evolution reaction, an anode for the oxygen evolution reaction, and a chassis for managing the flows of a liquid electrolyte and the product gas streams. Absent from this device is an ionically conducting membrane, a key component in a conventional polymer electrolyte membrane (PEM) electrolyzer that typically serves as a physical barrier for separating product gases generated at the anode and cathode. These membranes can allow for compact and efficient electrolyzer designs, but are prone to degradation and failure if exposed to impurities in the electrolyte. A membraneless electrolyzer has the opportunity to reduce capital costs and operate in non-pristine environments, but little is known about the performance limitations and design rules that govern operation of membraneless electrolyzers. These design rules require a thorough understanding of the thermodynamics, kinetics, and transport processes in electrochemical systems. In Chapter 2, these concepts are reviewed and a framework is provided to guide the continuum scale modeling of the performance of membraneless electrochemical cells. Afterwards, three different studies are presented which combine experiment and theory to demonstrate the mechanisms of product transport and efficiency loss. Chapter 3 investigates the dynamics of hydrogen bubbles during operation of a membraneless electrolyzer, which can strongly affect the product purity of the collected hydrogen. High-speed video imaging was implemented to quantify the size and position of hydrogen gas bubbles as they detach from porous mesh electrodes. The total hydrogen detected was compared to the theoretical value predicted by Faraday’s law. This analysis confirmed that not all electrochemically generated hydrogen enters the gas phase at the cathode surface. In fact, significant quantities of hydrogen remain dissolved in solution, and can result in lower product collection efficiencies. Differences in bubble volume fraction evolved along the length of the cathode reflect differences in the local current densities, and were found to be in agreement with the primary current distribution. Overall, this study demonstrates the ability to use in-situ HSV to quantitatively evaluate key performance metrics of membraneless electrolyzers in a non-invasive manner. This technique can be of great value for future experiments, where statistical analysis of bubble sizes and positions can provide information on how to collect hydrogen at maximum purity. Chapter 4 presents an electrode design where selective placement of the electrocatalyst is shown to enhance the purity of hydrogen collected. These “asymmetric electrodes” were prepared by coating only one planar face of a porous titanium mesh electrode with platinum electrocatalyst. For an opposing pair of electrodes, the platinum coated surface faces outwards such that the electrochemically generated bubbles nucleate and grow on the outside while ions conduct through the void spacing in the mesh and across the inter-electrode gap. A key metric used in evaluating the performance of membraneless electrolyzers is the hydrogen cross-over percentage, which is defined as the fraction of electrochemically generated hydrogen that is collected in the headspace over the oxygen-evolving anode. When compared to the performance of symmetric electrodes – electrodes coated on both faces with platinum – the asymmetric electrodes demonstrated significantly lower rates of cross-over. With optimization, asymmetric electrodes were able to achieve hydrogen cross-over values as low as 1%. These electrodes were then incorporated into a floating photovoltaic electrolysis device for a direct demonstration of solar driven electrolysis. The assembled “solar fuels rig” was allowed to float in a reservoir of 0.5 M sulfuric acid under a light source calibrated to simulate sunlight, and a solar to hydrogen efficiency of 5.3% was observed. In Chapter 5, the design principles for membraneless electrolyzers were applied to a photoelectrochemical (PEC) cell. Whereas an electrolyzer is externally powered by electricity, a PEC cell can directly harvest light to drive an electrochemical reaction. The PEC reactor was based on a parallel plate design, where the current was demonstrated to be limited by the intensity of light and the concentration of the electrolyte. By increasing the average flow rate of the electrolyte, mass transport limitations could be alleviated. The limiting current density was compared to theoretical values based off of the solution to a convection-diffusion problem. This modeled solution was used to predict the limitations to PEC performance in scaled up designs, where solar concentration mirrors could increase the total current density. The mass transport limitations of a PEC flow cell are also highly relevant to the study of CO2 reduction, where the solubility limit of CO2 in aqueous electrolyte can also limit performance.

C'est la surface, et non le matériau qui interagit avec l'environnement. Par conséquent, en modifiant la surface d'un matériau de manière contrôlée, nous pouvons moduler ces interactions avec son environnement. Les sels d'aryles diazonium semblent très adaptés pour modifier les propriétés de surface de matériaux de par leurs diversités structurelles et leur capacité à modifier des surfaces conductrices par électrochimie. Ce travail de thèse se concentre sur l'étude du transfert électronique au travers de couches organiques de différentes épaisseurs (monocouches, couches ultraminces et multicouches), générées par électro-réduction de sels d'aryles diazonium. La molécule électroactive étudiée peut être alors soit fixée à la surface du matériau ou en solution. Différentes méthodes électrochimiques ont été utilisées au cours de cette thèse : CV, EIS et SECM. Dans un premier temps, l'étude des propriétés électrochimiques de surfaces carbonées modifiées par des monocouches d'alkyle-ferrocène a été entreprise dans différents solvants ; ainsi que leur évaluation pour des applications en stockage d'énergie. La deuxième étude s'intéresse à l'utilisation d'une approche « bottom-up » pour la fabrication de surfaces organisées. Des substrats de carbone et d'or ont été modifiés par électro-réduction d'un sel d'aryle diazonium pré-organisé en forme de tétraèdre. Ceci aboutit à l'obtention d'un film organique ultra-mince possédant des propriétés de tamisage moléculaire et de rectification de courant électrochimique vis-à-vis de sondes redox en solution. La troisième étude s'est ensuite focalisée sur la réaction de réduction du dioxygène et de ses intermédiaires, qui présentent un intérêt général aussi bien dans des processus naturels qu'en industrie. La détection de ces intermédiaires a été entreprise par SECM, utilisant une stratégie « d'empreinte » utilisant différentes couches organiques sensibles. L'influence du potentiel appliqué et de l'électrolyte a été étudiée. Dans ce travail, nous avons démontré que les propriétés électrochimiques de sondes redox en solution ou greffées à la surface d'un matériau peuvent être modulées par l'utilisation de couches organiques. Ces recherches fondamentales présentent un intérêt dans des domaines tels que le stockage d'énergie et la catalyse. / It is the surface, not the bulk material that interacts with the surrounding environment; hence by altering the surface in a controlled manner we can modulate the properties of the material towards its environment. Aryldiazonium salts are suitable to tailor the surface properties since their structural diversity and their electrochemically-assisted bonding ability to modified conducting surfaces. This thesis focuses on the study of the electron transfer through different aryl layers by aryldiazonium electro-reduction at three different thickness levels, monolayer, near-monolayer, and multilayer, when the electroactive molecule is attached to the surface or in solution. Three different electrochemical methods have been used throughout this thesis, CV, EIS and SECM. The first study of this thesis focused on the investigation of the electrochemical properties of alkyl-ferrocene on-carbon monolayers in different solvents and its evaluation for improving the global charge density of carbon materials for energy storage applications. The second study used a bottom-up approach for the fabrication of well-organized surfaces. Carbon and gold substrates were modified by electro-reduction of a tetrahedral-shape preorganized aryldiazonium salt resulting in an ultrathin organic film that showed molecular sieving and current rectification properties towards redox probes in solution. The third study then focused on the oxygen reduction reaction and its intermediates, which are of general importance in natural and industrial processes. Detection of intermediates was achieved by SECM in a foot-printing strategy based on the use of different sensitive aryl multilayers. The role of the applied potential and electrolytes was investigated. Here we have demonstrated that the electrochemical properties of redox probes attached to a surface or in solution can be modulated by introducing aryl layers allowing fundamental research investigations of interest in fields such as energy storage and catalysis.

In this study, it was investigated how individual households could manage security of supply during an outage by installing a local energy system that could operate independently from the electricity grid. By installing local renewable off-grid energy systems, households could guarantee an uninterrupted supply of energy even during an outage on the electricity grid, while also increasing their energy autonomy during normal circumstances. The results showed that managing an outage during summer was fairly easy. Due to high electricity production, a small energy storage was enough to manage an outage during summer. However, managing an outage during winter was more critical. During winter, the systems needed to be almost fully reliant on the energy storage. This significantly increased the cost of these systems. Due to the high cost for the energy systems today, it was not considered a feasible solution to improve energy security at a national level. However, at a local level, this was considered to have the potential to improve energy security. First, it could to be of interest for people who already have installed solar panels, who could add a battery and thereby be able to manage an outage during summer. Second, it could be of interest for people who are more exposed to outages or have a low trust in the system to work properly. Lastly, this could be of interest for actors for whom backup energy is important, for instance for the industry.

Submitted by Silvana Teresinha Dornelles Studzinski (sstudzinski) on 2015-10-26T16:14:39Z No. of bitstreams: 1 Jutaí Juarez Estrázulas_.pdf: 1716303 bytes, checksum: ac095da5508e03eaab20ab1008f22067 (MD5) / Made available in DSpace on 2015-10-26T16:14:39Z (GMT). No. of bitstreams: 1 Jutaí Juarez Estrázulas_.pdf: 1716303 bytes, checksum: ac095da5508e03eaab20ab1008f22067 (MD5) Previous issue date: 2015-06-12 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Inúmeras aplicações residenciais, comerciais e industriais voltadas ao gerenciamento térmico tem seus custos operacionais reduzidos quando um sistema de armazenamento de energia térmica é incorporado. Tal tipo de sistema pode, por exemplo, absorver energia térmica oriunda de fonte solar, de reaproveitamento de calor de processo industrial ou mesmo proveniente de energia elétrica (nos horários em que esta é menos onerosa), e liberá-la em um horário em que estas fontes de calor não estejam presentes e em que a energia elétrica, se utilizada, seria mais onerosa.Os PCMs (Phase Change Materials), devido ao seu alto calor latente de fusão, são materiais que representam uma alternativa viável à implementação de sistemas de armazenamento de energia térmica. No entanto, inúmeros PCMs ainda não tiveram suas características e propriedades fluidodinâmicas investigadas suficientemente. Assim, este trabalho apresenta um estudo numérico da mudança de fasede PCMs da família RT,em cavidades cilíndricas, visando o armazenamento térmico de energia através de calor latente (LHTES). O estudo foi realizado através de simulação numérica por CFD, com o software ANSYS Fluent. O modelo numérico adotado é bidimensional e é composto pelas equações da conservação da massa, quantidade de movimento e energia. Além destas, foi utilizada a técnica de modelamento entalpia-porosidade. A malha computacional é do tipo hexaédrica, com refinamento junto às paredes da geometria e na região de interface entre o PCM e o ar. O modelo implementado foi validado com resultados numéricos e experimentais da literatura, obtendo-se bons resultados. Foi avaliado o processo de fusão de cinco diferentes tipos de PCMs (RT 4, RT 35, RT 35HC (alta capacidade), RT 55 e RT 82), cada um deles com três intervalos de temperatura (T=10, 20 e 30 °C).Além disto, para T=10 ºC, os PCMS RT 27, RT 35, RT 35 HC e RT 82 foram testados para cinco diferentes valores de constante C (Mushy Zone), totalizando trinta diferentes situações. Paraos PCMs RT 4, RT 35, RT55 e RT82, aumentando-se o T de 10 oC para 20 oC e de 10 oC para 30 oC, para frações líquidas entre 0,4 e 0,8, a redução média dos tempos de fusão foide, aproximadamente, 55,8% e 71,8% e os incrementos médios no fluxo de calor foram de 63% e 111 %, respectivamente. Para o RT35HC, as reduções médias nos tempos de fusão foram de 51,6% e de 67,8%, para a mesma faixa de fração líquidae mesmos T. O RT35HC, quando comparado com o RT 35, possui calor latente de fusão 41,1% maiore os seus tempos de fusão são entre 100% à 134% superiores, dependendo do T utilizado. / Several residential, commercial and industrial applications focused on thermal management have their operating costs reduced when a thermal energy storage system is incorporated to them. This type of system can provide, can, for example, absorb thermal energy from solar source, heat reuse from industrial process or even from electrical power (during the time this is less expensive) and release it at a time that these heat sources are not present and the electrical power, if used, would be more expensive.The Phase Change Materials (PCMs), due to their high latent heat of fusion, are materials that represent a viable alternative to the implementation of thermal energy storage systems. However, many PCMs have not had their characteristics and fluid dynamics properties sufficiently investigated. Thus, this paper presents a numerical study of RT phase change materials family, inside cylindrical cavities, aiming at the thermal energy storage trough latent heat (LHTES). The study was conducted through a CFD numerical simulation, with ANSYS Fluent software. The numeric model adopted is two-dimensional and is composed by mass conservation, movement amount and energy equations. In addition, the enthalpy-porosity modeling technique was used. The computational mesh is hexaedric, with refinement along the walls of geometry and at the interface area between the PCM and air. The model was validated with numerical and experimental results available in the literature, achieving good results. The fusion process of five different PCMs (RT 4, RT 35, RT 35 HC (high capacity), RT 55 and RT 82) was evaluated, each one of them with three temperature ranges (T= 10, 20 e 30 °C). Furthermore, for T=10 °C, the PCMs RT 27, RT 35, RT 35 HC and RT 82 were tested for five different values of C constant (Mushy Zone) totaling thirty different situations. For PCMs RT 4, RT 35, RT 55 and RT 82, increasing T from 10 oC to 20 oC and from 10 oC to 30 oC, for liquid fraction between 0,4 and 0,8, the average reduction in fusion time were, approximately, 55.8% and 71.8% and the average increase in heat flow were 63% and 111% respectively. For RT 35 HC, the average reductions in fusion time were 51.6% and 67.8% for the same liquid fraction range and same T. The RT 35 HC, when compared to RT 35, has latent heat of fusion 41.1% greater and its fusion times are between 100% to 134% greater, depending on T used.

SAMMANFATTNING Medvetenhet och oro kring miljöeffekter från utsläpp av växthusgaser och de minskande resurserna av icke förnybara energikällor har ökat de senaste årtiondena. Utvecklingen av ny teknologi för förnybar energi har drivits fram globalt som ett svar på denna oro. Det har skett stora framsteg i produktion av el och värme från sol, vind, hav, vattenkraft, biomassa, geotermiska resurser, biobränslen och väte. Följaktligen har utvecklingen av energi-lager blivit en viktig del för integration av förnybar energi i systemen. Det är gynnsamt för hela försörjningskedjan, för pålitlighet och bättre stabilitet i leveranser och distribution, och för ökad el-kvalitet. I uppsatsen undersöks en optimal energidesign för ett kombinerat system med vattenkraft och vindkraft inklusive ett lager i form av en damm. Vatten som pumpas upp till lagret har en stor och balanserande potential för att få in en högre grad förnybar energi i energisystemen. Detta är nödvändigt då dessa energikällor är intermittenta och variabla till sin natur. Ett av de studerade objekten är ett vattenkraftverk med pumpad damm, Tehri i Uttarakhand, Indien. Systemets totala verkningsgrad om 93 % diskuteras utifrån förluster såväl som potentialen för vind och dess inverkan. Vind-data är hämta från National Institute of Wind Energy (NIWE) och har analyserats med programmen MATLAB och WindPro. Det slutligen valda området för exploatering av vindkraft blev Ramakkalmedu, Idukki district, Kerala, Indien. Efter valet av plats valdes tre olika vindturbiner ut för analys; Siemens SWT-3.2-113 3.2 MW, Enercon E-126 4.2MW, och Enercon E-126 7.58MW. Analysen består av flera delar; vindparks-modellering, beräkning av buller-generering från vindkraften, beräkning av årlig energi-generering - Annual Energy Production (AEP), kapacitetsfaktor, vindparkens effektivitet med hänsyn tagen till lagret/dammens variation av bas-last. Resultat har erhållits från alla tre turbinerna och den övergripande slutsatsen är att kombinationen med vatten- och vindkraft med lagring av vatten som pumpas upp vid behov är en tillfredsställande metod för att möta belastningstoppar, vilket valideras av denna uppsats.   Nyckelord: pumpade vattenkraftdammar, vindkraftparker, energi lager, förnybar energi. / ABSTRACT  Awareness and concern regarding the environmental effects of greenhouse gas emissions and depletion of non-renewable energy sources has increased over the last decades. A considerable development of new technology for renewable energy has occurred globally as an answer to this concern. There has been a major progress in production of electricity and heat generated from solar, wind, ocean, hydropower, biomass, geothermal resources, and biofuels and hydrogen. Consequently, the development of energy storages has become an imperative part, for integration of renewable energy. It is beneficial for the entire supply chain, for dependability and better stability, and for enhanced quality of electrical power. This thesis is exploring an optimal energy design for a system of pumped hydro-wind power plants including storage. Solutions with Pumped Hydro Storages have a great potential for their balancing role necessary for a higher degree of renewable energy sources, RES, in the energy systems because of the intermittent and variable nature of these sources. Tehri pumped hydro storage plant, in Uttarakhand, India is one of the objects studied in this thesis. The systems total efficiency of 93%, calculated from head losses, is discussed as well as wind potential and its impact. Wind data is obtained from National Institute of Wind Energy (NIWE) and analysed using the software tools MATLAB and WindPro. The finally chosen area explored for wind potential is Ramakkalmedu, Idukki district, Kerala, India. After selection of site within the area, three different turbines; Siemens SWT-3.2-113 3.2 MW, Enercon E-126 4.2MW, and Enercon E-126 7.58MW were considered for analysis. The analysis consists of several parts; Wind farm modelling, Noise estimation of Wind Park, estimation of Annual Energy Production (AEP), Capacity factor, Wind park efficiency with respect to the storage/reservoir´s base load variation. Results are achieved for all three turbines. The overall conclusion is that combined hydro and wind power with a pumped storage, is a satisfactory method for bulk energy store to address peak loads, which is validated by this thesis.   Keywords: Pumped Hydro, Wind farm, Energy Storage, Renewable Energy.

Off-grid hybrid renewable energy systems are known as an attractive and sustainable solution for supplying clean electricity to autonomous consumers. Typically, this applies to the communities that are located in remote or islanded areas where it is not cost-effective to extend the grid facilities to these regions. In addition, the use of diesel generators for electricity supply in these remote locations are proven to be uneconomical due to the difficult terrain which translates into high fuel transportation costs. The use of renewable energy sources, coupling with the diesel generator allows for the diesel fuel to be offset. However, to date, a common design standard for the off-grid system has yet to be found and some challenges still exist while attempting to design a reliable system. These include the sizing of hybrid systems, coordination between the operation of dissimilar power generators and the fluctuating load demands, optimal utilisation of the renewable energy resources and identifying the underlying principles which reduce the reliability of the off-grid systems. In order to address these challenges, this research has first endeavoured into developing a sizing algorithm which particularly seeks the optimal size of the batteries and the diesel generator usage. The batteries and diesel generator function in filling the gap between the power generated from the renewable energy resources and the load demand. Thus, the load requirement is also an important factor in determining the cost-effectiveness of the overall system in the long run. A sensitivity analysis is carried out to provide a better understanding of the relationship between the assessed renewable energy resources, the load demand, the storage capacity and the diesel generator fuel usage. The thesis also presents the modelling, simulation and experimental work on the proposed hybrid wind-diesel-battery system. These are being implemented with a full-scale system and they are based on the off-the-shelf components. A novel algorithm to optimise the operation of a diesel generator is also proposed. The steady-state and dynamic analysis of the proposed system are presented, from both simulation and an experimental perspective. Three single-phase grid-forming inverters and a fixed speed wind turbine are used as a platform for case studies. The grid-forming inverters adopt droop control method which allows parallel operation of several grid-forming sources. Droop control-based inverters are known as independent and autonomous due to the elimination of intercommunication links among distributed converters. Moreover, the adopted fixed speed wind turbine employs a squirrel cage induction generator which is well known for its robustness, high reliability, simple operation and low maintenance. The results show a good correlation between the modelling, the experimental measurements, and the field tested results. The final stage of this research explores the effect of tower shadow on off-grid systems. Common tower designs for small wind turbine applications, which are the tubular and the lattice configurations, are considered in this work. They generate dissimilar tower shadow profiles due to the difference in structure. In this research, they are analytically modelled for a wind turbine which is being constructed as a downwind configuration. It is proven that tower shadow indeed brings negative consequence to the system, particularly its influence on battery lifetime within an off-grid system. This detrimental effect occurs when power generation closely matches the load demand. In this situation, small frequent charging and discharging cycles or the so called microcycles, take place. The battery lifetime reduction due to these microcycles has been quantified and it is proven that they are not negligible and should be taken into consideration while designing an off-grid hybrid system.

Photovoltaic (PV) system is one of the most prominent energy sources, producing electricity directly from sunlight. In additionally, it is easy to install and is supported financially by many governments as part of their strategy to reduce CO2 gas emissions, and to achieve their agreed set of reduction targets by 2020. In the meantime, researchers have been working on the PV system to make it more efficient, easy to maintain, reliable to use and cost effective. In the stand-alone PV system, a battery is required. This is due to the fluctuating nature of the output energy delivered by the PV arrays owing to the weather conditions and the unpredictable behaviour of uses with regard to the consumption of energy. During the hours of sunshine, the PV system is directly feeding the load and any surplus electrical energy is stored in the battery at a constant current. During the night, or during a period of low solar irradiation, the energy is supplied to the load from the battery. However, the stand-alone PV system is designed to provide an acceptable balance between reliability and cost, which is a major challenge to the designer owing to the approaches used to size the PV arrays and the battery bank. As a result, the unpredictable, quick daily changes on the PV output is not dependable. Moreover, battery performance, length of life and energy efficiency depends on the rate at which it is discharged. Therefore, it is essential to use other methods to deal with any quick variation in energy. In this thesis, a super capacitor is used to solve this problem, as it can deal with the fast-changing weather, or a rapid variation in the energy requirements of the customer. A critical evaluation with in-depth analysis of the placement and the implementation for the super-capacitor in the PV standalone system has been carried out. The results show, super-capacitor capacitance and the converter efficiency affect the delivered load energy. However, the bi-directional topology performs better than uni-directional under the same conditions. Finally, a further improvement of the system at component level, has been developed through an energy recovery snubber for the switching transition and achieved a recovery of energy for the resistive load, 94.44% for the turn on transition and 92.86% for the turn off transition. Moreover, for the inductive load, 78.33% and 97.33% of energy has been recovered for the turn on and for the turn off transition respectively.

Supercapacitors, also known as electrochemical capacitors, have shown great potential as energy storage devices; and 3D printing likewise as a manufacturing technique. This research progressively investigates combining these two technologies to fabricate 3D-printed, electrochemical double-layer capacitors (EDLCs). Small EDLCs were designed in a sandwich structure with an FDM-printed plastic frame and carbon electrodes. Inkjet printing was initially combined with FDM printing to produce a pilot sample with a silver ink current collector, however this performed poorly (Cs = 6 mF/g). Henceforth a paste extrusion system was added to the FDM printer to deposit the current collectors and electrodes, fabricating the entire device in a single continuous process. This process was progressively developed and tested, ultimately attaining specific capacitances of 200 mF/g. The fully integrated 3D printing process used to manufacture the EDLCs was a novel approach. Combining the FDM printer with a paste extruder allowed for a high degree of dimensional accuracy, as well as simplifying the production process. This aspect of the design functioned successfully, without significant faults, and proved a reliable fabrication method. The later designs used in this study provided the EDLCs extendable by incorporating connection jacks. This was to create the possibility to increase capacitance simply by connecting multiple EDLCs together. Tests of this feature showed that it worked well, with the extendable EDLCs delivering outputs very close to the theoretical maximum efficiency of the unit. Carbon conductive paint was applied as a current collector and electrode for the 3D printed EDLCs in an exploration of metal-free 3D printed supercapacitors. These metal-free EDLCs were found to provide around 60% of the specific capacitance of the best performing EDLC variant produced (silver paint current collectors with activated carbon and carbon paint mixture electrodes). Although considerable improvement is required to produce EDLC samples with comparable capacitances to existing commercial manufacturing techniques, this study lays important groundwork in this area, and has introduces effective and innovative design ideas for supercapacitors and integrated 3D printing processes.