Propiedades Eléctricas en Membranas de Complejos Electrolitos Poliméricos PVA-OH/LI2SO4/PEG400

Lithium ion conducting polymer electrolytes based on polyvinyl Alcohol (PVA-OH) complexed with salt Li2SO4 and different weight percent ratios of PEG(400) plasticizer have been prepared by solution cast technique using deionized water as solvent. The thermogravimetric analysis (TGA) showed that the thermal stability of the materials depended on the plasticizer content. The FTIR study confirmed the polymer salt complex formation. The modulus spectra indicated the non-Debye nature of the material; a dominant relaxation process is visible being associated with the dynamic glass transition, relaxation-a. The maximum of each peak is shifted to higher frequencies as the plasticizer increases due to an enhancement of dipolar mobility in the origin of cooperative motions. A power law frequency dependence of the real part of the electrical conductivity is observed, which is characteristic of the effects of ion-ion and/or ion-chain correlations in ion motion. This variation is well fitted to a Jonscher's expression.

Desenvolvimento de conjunto membrana-eletrodos para célula a combustível de metanol direto passiva

Direct methanol fuel cells (DMFCs) without external pumps or other ancillary devices for fuel and oxidant supply are known as passive DMFCs and are potential candidates to replace lithium-ion batteries in powering portable electronic devices. This paper presents the results obtained from a membrane electrode assembly (MEA) specifically designed for passive DMFCs. Appropriated electrocatalysts were prepared and the effect of their loadings was investigated. Two types of gas diffusion layers (GDL) were also tested. The influence of the methanol concentration was analyzed in each case. The best MEA performance presented a maximum power density of 11.94 mW cm^-2.

Electrode Materials for Ionic Liquid Based-Supercapacitors

The development of safe, high energy and power electrochemical energy-conversion systems can be a response to the worldwide demand for a clean and low-fuel-consuming transport. This thesis work, starting from a basic studies on the ionic liquid (IL) electrolytes and carbon electrodes and concluding with tests on large-size IL-based supercapacitor prototypes demonstrated that the IL-based asymmetric configuration (AEDLCs) is a powerful strategy to develop safe, high-energy supercapacitors that might compete with lithium-ion batteries in power assist-hybrid electric vehicles (HEVs). The increase of specific energy in EDLCs was achieved following three routes: i) the use of hydrophobic ionic liquids (ILs) as electrolytes; ii) the design and preparation of carbon electrode materials of tailored morphology and surface chemistry to feature high capacitance response in IL and iii) the asymmetric double-layer carbon supercapacitor configuration (AEDLC) which consists of assembling the supercapacitor with different carbon loadings at the two electrodes in order to exploit the wide electrochemical stability window (ESW) of IL and to reach high maximum cell voltage (Vmax). Among the various ILs investigated the N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR1(2O1)TFSI) was selected because of its hydrophobicity and high thermal stability up to 350 °C together with good conductivity and wide ESW, exploitable in a wide temperature range, below 0°C. For such exceptional properties PYR1(2O1)TFSI was used for the whole study to develop large size IL-based carbon supercapacitor prototype. This work also highlights that the use of ILs determines different chemical-physical properties at the interface electrode/electrolyte with respect to that formed by conventional electrolytes. Indeed, the absence of solvent in ILs makes the properties of the interface not mediated by the solvent and, thus, the dielectric constant and double-layer thickness strictly depend on the chemistry of the IL ions. The study of carbon electrode materials evidences several factors that have to be taken into account for designing performing carbon electrodes in IL. The heat-treatment in inert atmosphere of the activated carbon AC which gave ACT carbon featuring ca. 100 F/g in IL demonstrated the importance of surface chemistry in the capacitive response of the carbons in hydrophobic ILs. The tailored mesoporosity of the xerogel carbons is a key parameter to achieve high capacitance response. The CO2-treated xerogel carbon X3a featured a high specific capacitance of 120 F/g in PYR14TFSI, however, exhibiting high pore volume, an excess of IL is required to fill the pores with respect to that necessary for the charge-discharge process. Further advances were achieved with electrodes based on the disordered template carbon DTC7 with pore size distribution centred at 2.7 nm which featured a notably high specific capacitance of 140 F/g in PYR14TFSI and a moderate pore volume, V>1.5 nm of 0.70 cm3/g. This thesis work demonstrated that by means of the asymmetric configuration (AEDLC) it was possible to reach high cell voltage up to 3.9 V. Indeed, IL-based AEDLCs with the X3a or ACT carbon electrodes exhibited specific energy and power of ca. 30 Wh/kg and 10 kW/kg, respectively. The DTC7 carbon electrodes, featuring a capacitance response higher of 20%-40% than those of X3a and ACT, respectively, enabled the development of a PYR14TFSI-based AEDLC with specific energy and power of 47 Wh/kg and 13 kW/kg at 60°C with Vmax of 3.9 V. Given the availability of the ACT carbon (obtained from a commercial material), the PYR1(2O1)TFSI-based AEDLCs assembled with ACT carbon electrodes were selected within the EU ILHYPOS project for the development of large-size prototypes. This study demonstrated that PYR1(2O1)TFSI-based AEDLC can operate between -30°C and +60°C and its cycling stability was proved at 60°C up to 27,000 cycles with high Vmax up to 3.8 V. Such AEDLC was further investigated following USABC and DOE FreedomCAR reference protocols for HEV to evaluate its dynamic pulse-power and energy features. It was demonstrated that with Vmax of 3.7 V at T> 30 °C the challenging energy and power targets stated by DOE for power-assist HEVs, and at T> 0 °C the standards for the 12V-TSS and 42V-FSS and TPA 2s-pulse applications are satisfied, if the ratio wmodule/wSC = 2 is accomplished, which, however, is a very demanding condition. Finally, suggestions for further advances in IL-based AEDLC performance were found. Particularly, given that the main contribution to the ESR is the electrode charging resistance, which in turn is affected by the ionic resistance in the pores that is also modulated by pore length, the pore geometry is a key parameter in carbon design not only because it defines the carbon surface but also because it can differentially “amplify” the effect of IL conductivity on the electrode charging-discharging process and, thus, supercapacitor time constant.

Controllable assembly of graphene hybrid materials and their application in energy storage and conversion

Hybrid Elektrodenmaterialien (HEM) sind der Schlüssel zu grundlegenden Fortschritten in der Energiespeicherung und Systemen zur Energieumwandlung, einschließlich Lithium-Ionen-Batterien (LiBs), Superkondensatoren (SCs) und Brennstoffzellen (FCs). Die faszinierenden Eigenschaften von Graphen machen es zu einem guten Ausgangsmaterial für die Darstellung von HEM. Jedoch scheitern traditionelle Verfahren zur Herstellung von Graphen-HEM (GHEM) scheitern häufig an der fehlenden Kontrolle über die Morphologie und deren Einheitlichkeit, was zu unzureichenden Grenzflächenwechselwirkungen und einer mangelhaften Leistung des Materials führt. Diese Arbeit konzentriert sich auf die Herstellung von GHEM über kontrollierte Darstellungsmethoden und befasst sich mit der Nutzung von definierten GHEM für die Energiespeicherung und -umwandlung. Die große Volumenausdehnung bildet den Hauptnachteil der künftigen Lithium-Speicher-Materialien. Als erstes wird ein dreidimensionaler Graphen Schaumhybrid zur Stärkung der Grundstruktur und zur Verbesserung der elektrochemischen Leistung des Fe3O4 Anodenmaterials dargestellt. Der Einsatz von Graphenschalen und Graphennetzen realisiert dabei einen doppelten Schutz gegen die Volumenschwankung des Fe3O4 bei dem elektrochemischen Prozess. Die Leistung der SCs und der FCs hängt von der Porenstruktur und der zugänglichen Oberfläche, beziehungsweise den katalytischen Stellen der Elektrodenmaterialien ab. Wir zeigen, dass die Steuerung der Porosität über Graphen-basierte Kohlenstoffnanoschichten (HPCN) die zugängliche Oberfläche und den Ionentransport/Ladungsspeicher für SCs-Anwendungen erhöht. Desweiteren wurden Stickstoff dotierte Kohlenstoffnanoschichten (NDCN) für die kathodische Sauerstoffreduktion (ORR) hergestellt. Eine maßgeschnittene Mesoporosität verbunden mit Heteroatom Doping (Stickstoff) fördert die Exposition der aktiven Zentren und die ORR-Leistung der metallfreien Katalysatoren. Hochwertiges elektrochemisch exfoliiertes Graphen (EEG) ist ein vielversprechender Kandidat für die Darstellung von GHEM. Allerdings ist die kontrollierte Darstellung von EEG-Hybriden weiterhin eine große Herausforderung. Zu guter Letzt wird eine Bottom-up-Strategie für die Darstellung von EEG Schichten mit einer Reihe von funktionellen Nanopartikeln (Si, Fe3O4 und Pt NPs) vorgestellt. Diese Arbeit zeigt einen vielversprechenden Weg für die wirtschaftliche Synthese von EEG und EEG-basierten Materialien.

Preparation of silicon-metal nanocomposites based on electrophoretic deposition

Silicon has long been considered as one of the most promising anode material for lithium-ion batteries. However, the poor cycle life due to stress during charge/discharge cycling has been a major concern for its practical applications. In this report, novel Si-metal nanocomposites have been explored to accommodate the stress generated in the intercalation process. Several approaches have been studied with the aim of getting uniform mixing, good mechanical stability and high Si content. Among the three approaches being investigated, Si- Galinstan nanocomposite based on electrophoretic deposition showed the best promise by achieving at least 32.3% Si theoretical weight percentage, and our in current experiments we’ve already get 13% Silicon weight percentage, which gave us an anode material 46% more capacity than the current commercial product.

NANOSCALE ELECTROCHEMISTRY BY IN-SITU TRANSMISSION ELECTRON MICROSCOPY

Nanoscale research in energy storage has recently focused on investigating the properties of nanostructures in order to increase energy density, power rate, and capacity. To better understand the intrinsic properties of nanomaterials, a new and advanced in situ system was designed that allows atomic scale observation of materials under external fields. A special holder equipped with a scanning tunneling microscopy (STM) probe inside a transmission electron microscopy (TEM) system was used to perform the in situ studies on mechanical, electrical, and electrochemical properties of nanomaterials. The nanostructures of titanium dioxide (TiO2) nanotubes are characterized by electron imaging, diffraction, and chemical analysis techniques inside TEM. TiO2 nanotube is one of the candidates as anode materials for lithium ion batteries. It is necessary to study their morphological, mechanical, electrical, and electrochemical properties at atomic level. The synthesis of TiO2 nanotubes showed that the aspect ratio of TiO2 could be controlled by processing parameters, such as anodization time and voltage. Ammonium hydroxide (NH4OH) treated TiO2 nanotubes showed unexpected instability. Observation revealed the nanotubes were disintegrated into nanoparticles and the tubular morphology was vanished after annealing. The nitrogen compounds incorporated in surface defects weaken the nanotube and result in the collapse of nanotube into nanoparticles during phase transformation. Next, the electrical and mechanical properties of TiO2 nanotubes were studied by in situ TEM system. Phase transformation of anatase TiO2 nanotubes into rutile nanoparticles was studied by in situ Joule heating. The results showed that single anatase TiO2 nanotubes broke into ultrafine small anatase nanoparticles. On further increasing the bias, the nanoclusters of anatase particles became prone to a solid state reaction and were grown into stable large rutile nanoparticles. The relationship between mechanical and electrical properties of TiO2 nanotubes was also investigated. Initially, both anatase and amorphous TiO2 nanotubes were characterized by using I-V test to demonstrate the semiconductor properties. The observation of mechanical bending on TiO2 nanotubes revealed that the conductivity would increase when bending deformation happened. The defects on the nanotubes created by deformation helped electron transportation to increase the conductivity. Lastly, the electrochemical properties of amorphous TiO2 nanotubes were characterized by in situ TEM system. The direct chemical and imaging evidence of lithium-induced atomic ordering in amorphous TiO2 nanotubes was studied. The results indicated that the lithiation started with the valance reduction of Ti4+ to Ti3+ leading to a LixTiO2 intercalation compound. The continued intercalation of Li ions in TiO2 nanotubes triggered an amorphous to crystalline phase transformation. The crystals were formed as nano islands and identified to be Li2Ti2O4 with cubic structure (a = 8.375 Å). This phase transformation is associated with local inhomogeneities in Li distribution. Based on these observations, a new reaction mechanism is proposed to explain the first cycle lithiation behavior in amorphous TiO2 nanotubes.

Viabilidad técnica para la explotación y separación isotópica de Li y prospectiva en el mercado de baterías de ION-7Li y de 6Li como material base de diseño en reactores de fusión nuclear

En claro alineamiento con estrategias de sostenibilidad en el uso de recursos naturales en un escenario constante de aumento de la demanda energética mundial, el desarrollo de la tecnología energética en la Historia de la Especie Humana muestra un vector de evolución permanente desde su origen en el sentido del desarrollo y uso de nuevas fuentes energéticas con la explotación de recursos naturales de manera más eficiente: soluciones energéticas con aumento de la densidad energética (exoenergía de proceso por unidad de masa de recurso natural). Así el cambio de escala en la demanda de explotación del Litio como recurso natural se viene presentando en la última década ligada al desarrollo del mercado de las baterías "ion-Litio" y los requisitos de combustible (Deuterio y Litio) en el camino de la fusión nuclear como opción energética próxima. El análisis anticipado de las demandas sinérgicas a escala de ambos mercados aparece de enorme interés prospectivo en sus aspectos técnicos: (1) tecnologías de base para la extracción mineral y de agua marina y (2) su enriquecimiento isotópico (de interés sinérgico; 7Li para baterías eficientes ion-litio; 6Li como regenerador de tritio en ciclo de combustible en fusión nuclear) a la vez que en sus aspectos económicos. Este Proyecto realiza: (1) un ejercicio de análisis prospectivo de la demanda y de mercado para el enriquecimiento 6Li/7Li para las próximas décadas, (2) se califican los desarrollos tecnológicos específicos que van a poder permitir la producción a escala conforme a la demanda; (3) se selecciona y califica una técnica [de centrifugación / termo-difusión/ destilación combinada] como opción tecnológicamente viable para la producción a escala de formas litiadas; (4) se propone un diseño conceptual de planta de producción y finalmente (5) propone un estudio de viabilidad para la demostración de proceso y construcción de dicha planta de demostración de la nueva capacidad tecnológica. ABSTRACT Clearly aligned with sustainability strategies under growing world energy demand in the use of natural resources the development of energy technology in the history of the human species shows a vector of ongoing evolution from its origin in the sense of the development and use of new energy sources with the exploitation of natural resources in a more efficient manner. The change of scale in the demand for exploitation of Lithium as a natural resource appears during the last decade as bound to the deployment of "lithium-ion" batteries market and to the Nuclear Fusion fuels (deuterium and lithium) supply scaled demands. The prospective analysis of demands to scale in both markets appears in scene with huge prospective interest in its technical aspects: (1) base technologies for mineral and water marine extraction (2) its isotopic enrichment (synergistic interests; 7Li efficient battery Li-ion; 6Li as fusion nuclear fuel breeder (tritium) as well as in its economic aspects. This Project: (1) propose a prospective analysis exercise of the synergistic supply demand for coming decades for the enrichment of 6Li and 7Li, (2) qualifies specific technological developments ongoing to respond to supply demand; (3) select and qualifies an appropriate technique [combined centrifugation/thermo-diffusion/distillation] as technologically viable option for lithiated forms scaled-production; (4) proposes a conceptual design of production plant based on the technique and finally (5) proposes a feasibility study for the process demonstration and construction of this new technological capability Demonstration Plant.

An open-source simulation tool of grid-connected PV systems.

This paper will present an open-source simulation tool, which is being developed in the frame of an European research project1. The tool, whose final version will be freely available through a website, allows the modelling and the design of different types of grid-connected PV systems, such as large grid-connected plants and building-integrated installations. The tool is based on previous software developed by the IES-UPM2, whose models and energy losses scenarios have been validated in the commissioning of PV projects3 carried out in Spain, Portugal, France and Italy, whose aggregated capacity is nearly 300MW. This link between design and commissioning is one of the key points of tool presented here, which is not usually addressed by present commercial software. The tool provides, among other simulation results, the energy yield, the analysis and breakdown of energy losses, and the estimations of financial returns adapted to the legal and financial frameworks of each European country. Besides, educational facilities will be developed and integrated in the tool, not only devoted to learn how to use this software, but also to train the users on the best design PV systems practices. The tool will also include the recommendation of several PV community experts, which have been invited to identify present necessities in the field of PV systems simulation. For example, the possibility of using meteorological forecasts as input data, or modelling the integration of large energy storage systems, such as vanadium redox or lithium-ion batteries. Finally, it is worth mentioning that during the verification and testing stages of this software development, it will be also open to the suggestions received from the different actors of the PV community, such as promoters, installers, consultants, etc.

Effect of composition, sonication and pressure on the rate capability of 5 V-LiNi0.5Mn1.5O4 composite cathodes

Positive composite electrodes having LiNi0.5Mn1.5O4 spinel as active material, a blend of graphite and carbon black for increasing the electrode electrical conductivity and either polyvinyldenefluoride (PVDF) or a blend of PVDF with a small amount of Teflon® (1 wt%) for building up the electrode. They have been processed by tape casting on an aluminum foil as current collector using the doctor blade technique. Additionally, the component blends were either sonicated or not, and the processed electrodes were compacted or not under subsequent cold pressing. Composites electrodes with high weight, up to 17 mg/cm2, were prepared and studied as positive electrodes for lithium-ion batteries. The addition of Teflon® and the application of the sonication treatment lead to uniform electrodes that are well-adhered to the aluminum foil. Both parameters contribute to improve the capacity drained at high rates (5C). Additional compaction of the electrode/aluminum assemblies remarkably enhances the electrode rate capabilities. At 5C rate, remarkable capacity retentions between 80% and 90% are found for electrodes with weights in the range 3–17 mg/cm2, having Teflon® in their formulation, prepared after sonication of their component blends and compacted under 2 tonnes/cm2.

Ultra high temperature latent heat energy storage and thermophotovoltaic energy conversion

A conceptual energy storage system design that utilizes ultra high temperature phase change materials is presented. In this system, the energy is stored in the form of latent heat and converted to electricity upon demand by TPV (thermophotovoltaic) cells. Silicon is considered in this study as PCM (phase change material) due to its extremely high latent heat (1800 J/g or 500 Wh/kg), melting point (1410 C), thermal conductivity (~25 W/mK), low cost (less than $2/kg or $4/kWh) and abundance on earth. The proposed system enables an enormous thermal energy storage density of ~1 MWh/m3, which is 10e20 times higher than that of lead-acid batteries, 2e6 times than that of Li-ion batteries and 5e10 times than that of the current state of the art LHTES systems utilized in CSP (concentrated solar power) applications. The discharge efficiency of the system is ultimately determined by the TPV converter, which theoretically can exceed 50%. However, realistic discharge efficiencies utilizing single junction TPV cells are in the range of 20e45%, depending on the semiconductor bandgap and quality, and the photon recycling efficiency. This concept has the potential to achieve output electric energy densities in the range of 200-450 kWhe/m3, which is comparable to the best performing state of the art Lithium-ion batteries.

Investigação do mecanismo cinético da reação de redução de oxigênio em solventes não aquosos

O aumento no consumo energético e a crescente preocupação ambiental frente à emissão de gases poluentes criam um apelo mundial favorável para pesquisas de novas tecnologias não poluentes de fontes de energia. Baterias recarregáveis de lítio-ar em solventes não aquosos possuem uma alta densidade de energia teórica (5200 Wh kg-1), o que as tornam promissoras para aplicação em dispositivos estacionários e em veículos elétricos. Entretanto, muitos problemas relacionados ao cátodo necessitam ser contornados para permitir a aplicação desta tecnologia, por exemplo, a baixa reversibilidade das reações, baixa potência e instabilidades dos materiais empregados nos eletrodos e dos solventes eletrolíticos. Assim, neste trabalho um modelo cinético foi empregado para os dados experimentais de espectroscopia de impedância eletroquímica, para a obtenção das constantes cinéticas das etapas elementares do mecanismo da reação de redução de oxigênio (RRO), o que permitiu investigar a influência de parâmetros como o tipo e tamanho de partícula do eletrocatalisador, o papel do solvente utilizado na RRO e compreender melhor as reações ocorridas no cátodo dessa bateria. A investigação inicial se deu com a utilização de sistemas menos complexos como uma folha de platina ou eletrodo de carbono vítreo como eletrodos de trabalho em 1,2-dimetoxietano (DME)/perclorato de lítio (LiClO4). A seguir, sistemas complexos com a presença de nanopartículas de carbono favoreceu o processo de adsorção das moléculas de oxigênio e aumentou ligeiramente (uma ordem de magnitude) a etapa de formação de superóxido de lítio (etapa determinante de reação) quando comparada com os eletrodos de platina e carbono vítreo, atribuída à presença dos grupos laterais mediando à transferência eletrônica para as moléculas de oxigênio. No entanto, foi observada uma rápida passivação da superfície eletrocatalítica através da formação de filmes finos de Li2O2 e Li2CO3 aumentando o sobrepotencial da bateria durante a carga (diferença de potencial entre a carga e descarga > 1 V). Adicionalmente, a incorporação das nanopartículas de platina (Ptnp), ao invés da folha de platina, resultou no aumento da constante cinética da etapa determinante da reação em duas ordens de magnitude, o qual pode ser atribuído a uma mudança das propriedades eletrônicas na banda d metálica em função do tamanho nanométrico das partículas, e estas modificações contribuíram para uma melhor eficiência energética quando comparado ao sistema sem a presença de eletrocatalisador. Entretanto, as Ptnp se mostraram não específicas para a RRO, catalisando as reações de degradação do solvente eletrolítico e diminuindo rapidamente a eficiência energética do dispositivo prático, devido ao acúmulo de material no eletrodo. O emprego de líquido iônico como solvente eletrolítico, ao invés de DME, promoveu uma maior estabilização do intermediário superóxido formado na primeira etapa de transferência eletrônica, devido à interação com os cátions do líquido iônico em solução, o qual resultou em um valor de constante cinética da formação do superóxido de três ordens de magnitude maior que o obtido com o mesmo eletrodo de carbono vítreo em DME, além de diminuir as reações de degradação do solvente. Estes fatores podem contribuir para uma maior potência e ciclabilidade da bateria de lítio-ar operando com líquidos iônicos.

Pseudocapacitance of zeolite-templated carbon in organic electrolytes

Carbon and graphene-based materials often show some amount of pseudocapacitance due to their oxygen-functional groups. However, such pseudocapacitance is generally negligible in organic electrolytes and has not attracted much attention. In this work, we report a large pseudocapacitance of zeolite-templated carbon (ZTC) based on the oxygen-functional groups in 1 M tetraethylammonium tetrafluoroborate dissolved in propylene carbonate (Et4NBF4/PC). Due to its significant amount of active edge sites, a large amount of redox-active oxygen functional groups are introduced into ZTC, and ZTC shows a high specific capacitance (330 F g−1). Experimental results suggest that the pseudocapacitance could be based on the formation of anion and cation radicals of quinones and ethers, respectively. Moreover, ZTC shows pseudocapacitance also in 1 M lithium hexafluorophosphate dissolved with a mixture of ethylene carbonate and diethyl carbonate (LiPF6/EC+DEC) which is used for lithium-ion batteries and lithium-ion capacitors.

Synthesis and electron emission properties of aligned carbon nanotube arrays

Carbon nanotubes (CNTs) have become one of the most interesting allotropes of carbon due to their intriguing mechanical, electrical, thermal and optical properties. The synthesis and electron emission properties of CNT arrays have been investigated in this work. Vertically aligned CNTs of different densities were synthesized on copper substrate with catalyst dots patterned by nanosphere lithography. The CNTs synthesized with catalyst dots patterned by spheres of 500 nm diameter exhibited the best electron emission properties with the lowest turn-on/threshold electric fields and the highest field enhancement factor. Furthermore, CNTs were treated with NH3 plasma for various durations and the optimum enhancement was obtained for a plasma treatment of 1.0 min. CNT point emitters were also synthesized on a flat-tip or a sharp-tip to understand the effect of emitter geometry on the electron emission. The experimental results show that electron emission can be enhanced by decreasing the screening effect of the electric field by neighboring CNTs. In another part of the dissertation, vertically aligned CNTs were synthesized on stainless steel (SS) substrates with and without chemical etching or catalyst deposition. The density and length of CNTs were determined by synthesis time. For a prolonged growth time, the catalyst activity terminated and the plasma started etching CNTs destructively. CNTs with uniform diameter and length were synthesized on SS substrates subjected to chemical etching for a period of 40 minutes before the growth. The direct contact of CNTs with stainless steel allowed for the better field emission performance of CNTs synthesized on pristine SS as compared to the CNTs synthesized on Ni/Cr coated SS. Finally, fabrication of large arrays of free-standing vertically aligned CNT/SnO2 core-shell structures was explored by using a simple wet-chemical route. The structure of the SnO2 nanoparticles was studied by X-ray diffraction and electron microscopy. Transmission electron microscopy reveals that a uniform layer of SnO2 is conformally coated on every tapered CNT. The strong adhesion of CNTs with SS guaranteed the formation of the core-shell structures of CNTs with SnO2 or other metal oxides, which are expected to have applications in chemical sensors and lithium ion batteries.

Hybrid Power System Intelligent Operation and Protection Involving Plug-in Electric Vehicles

Two key solutions to reduce the greenhouse gas emissions and increase the overall energy efficiency are to maximize the utilization of renewable energy resources (RERs) to generate energy for load consumption and to shift to low or zero emission plug-in electric vehicles (PEVs) for transportation. The present U.S. aging and overburdened power grid infrastructure is under a tremendous pressure to handle the issues involved in penetration of RERS and PEVs. The future power grid should be designed with for the effective utilization of distributed RERs and distributed generations to intelligently respond to varying customer demand including PEVs with high level of security, stability and reliability. This dissertation develops and verifies such a hybrid AC-DC power system. The system will operate in a distributed manner incorporating multiple components in both AC and DC styles and work in both grid-connected and islanding modes. The verification was performed on a laboratory-based hybrid AC-DC power system testbed as hardware/software platform. In this system, RERs emulators together with their maximum power point tracking technology and power electronics converters were designed to test different energy harvesting algorithms. The Energy storage devices including lithium-ion batteries and ultra-capacitors were used to optimize the performance of the hybrid power system. A lithium-ion battery smart energy management system with thermal and state of charge self-balancing was proposed to protect the energy storage system. A grid connected DC PEVs parking garage emulator, with five lithium-ion batteries was also designed with the smart charging functions that can emulate the future vehicle-to-grid (V2G), vehicle-to-vehicle (V2V) and vehicle-to-house (V2H) services. This includes grid voltage and frequency regulations, spinning reserves, micro grid islanding detection and energy resource support. The results show successful integration of the developed techniques for control and energy management of future hybrid AC-DC power systems with high penetration of RERs and PEVs.

Litiumin talteenotto luonnon suola-altaista ionisilla nesteillä

Uusiutuvan energian käytön lisääntyminen lisää sähkön varastoinnin tarvetta. Litiumioniakku-jen on todettu olevan oivallisia keinoja varastoida sähköä esimerkiksi sähköautojen energian-lähteeksi. Tästä syystä akkujen kysyntä kasvaa nopeaa tahtia, jolloin nykyiset litiumlähteet ei-vät enää riitä tuottamaan tarpeeksi litiumia kasvavaan tarpeeseen. Tämän vuoksi litiumin tal-teenottoon tulee valjastaa uusia litiumin lähteitä, joiden hyödynnettävyys nykyisellä tekniikalla on pienen litiumkonsentraation ja muiden alkali- ja maa-alkalimetallien läsnäolon takia vaikeaa. Tällä hetkellä litiumia otetaan talteen eniten korkean litiumpitoisuuden luonnon suolajärvistä. Nykyisin käytössä oleva litiumin erotusprosessi on hidas ja sen käyttö pienten litiumkonsent-raatioiden suola-altailla on kannattamatonta. Tehokkaampana talteenottomenetelmänä luonnon suolajärvillä nähdään litiumin selektiivinen uutto ionisilla nesteillä. Menetelmä on todettu toi-mivaksi suolajärvillä, joilla on matala litiumkonsentraatio. Uusien suolajärvien käyttöönotto ei ratkaise kaikkia litiumin talteenottoon liittyviä ongelmia, sillä suolajärvet ovat alttiita ilmastonmuutokselle, eikä niiden litiumvarannot ole ehtymättömät. Merien litiumvarantoja sen sijaan pidetään lähes ehtymättöminä. Litiumin talteenotto meristä on mahdollista ionisia nesteitä ja membraaneja hyödyntävällä elektrodialyysilaitteistolla, jolla litiumia voidaan ottaa talteen myös hyvin pienistä pitoisuuksista. Lisäksi on mahdollista, että litiumin talteenottoon yhdistetään juomaveden valmistus. Tällainen vedenpuhdistusprosessi olisi myös hyvä kestävän kehityksen näkökulmasta.