New studies on the versatile roles of Polyaniline and its composites in polymer based optoelectronic and energy storage devices

From the early stages of the twentieth century, polyaniline (PANI), a well-known and extensively studied conducting polymer has captured the attention of scientific community owing to its interesting electrical and optical properties. Starting from its structural properties, to the currently pursued optical, electrical and electrochemical properties, extensive investigations on pure PANI and its composites are still much relevant to explore its potentialities to the maximum extent. The synthesis of highly crystalline PANI films with ordered structure and high electrical conductivity has not been pursued in depth yet. Recently, nanostructured PANI and the nanocomposites of PANI have attracted a great deal of research attention owing to the possibilities of applications in optical switching devices, optoelectronics and energy storage devices. The work presented in the thesis is centered around the realization of highly conducting and structurally ordered PANI and its composites for applications mainly in the areas of nonlinear optics and electrochemical energy storage. Out of the vast variety of application fields of PANI, these two areas are specifically selected for the present studies, because of the following observations. The non-linear optical properties and the energy storing properties of PANI depend quite sensitively on the extent of conjugation of the polymer structure, the type and concentration of the dopants added and the type and size of the nano particles selected for making the nanocomposites. The first phase of the work is devoted to the synthesis of highly ordered and conducting films of PANI doped with various dopants and the structural, morphological and electrical characterization followed by the synthesis of metal nanoparticles incorporated PANI samples and the detailed optical characterization in the linear and nonlinear regimes. The second phase of the work comprises the investigations on the prospects of PANI in realizing polymer based rechargeable lithium ion cells with the inherent structural flexibility of polymer systems and environmental safety and stability. Secondary battery systems have become an inevitable part of daily life. They can be found in most of the portable electronic gadgets and recently they have started powering automobiles, although the power generated is low. The efficient storage of electrical energy generated from solar cells is achieved by using suitable secondary battery systems. The development of rechargeable battery systems having excellent charge storage capacity, cyclability, environmental friendliness and flexibility has yet to be realized in practice. Rechargeable Li-ion cells employing cathode active materials like LiCoO2, LiMn2O4, LiFePO4 have got remarkable charge storage capacity with least charge leakage when not in use. However, material toxicity, chance of cell explosion and lack of effective cell recycling mechanism pose significant risk factors which are to be addressed seriously. These cells also lack flexibility in their design due to the structural characteristics of the electrode materials. Global research is directed towards identifying new class of electrode materials with less risk factors and better structural stability and flexibility. Polymer based electrode materials with inherent flexibility, stability and eco-friendliness can be a suitable choice. One of the prime drawbacks of polymer based cathode materials is the low electronic conductivity. Hence the real task with this class of materials is to get better electronic conductivity with good electrical storage capability. Electronic conductivity can be enhanced by using proper dopants. In the designing of rechargeable Li-ion cells with polymer based cathode active materials, the key issue is to identify the optimum lithiation of the polymer cathode which can ensure the highest electronic conductivity and specific charge capacity possible The development of conducting polymer based rechargeable Li-ion cells with high specific capacity and excellent cycling characteristics is a highly competitive area among research and development groups, worldwide. Polymer based rechargeable batteries are specifically attractive due to the environmentally benign nature and the possible constructional flexibility they offer. Among polymers having electrical transport properties suitable for rechargeable battery applications, polyaniline is the most favoured one due to its tunable electrical conducting properties and the availability of cost effective precursor materials for its synthesis. The performance of a battery depends significantly on the characteristics of its integral parts, the cathode, anode and the electrolyte, which in turn depend on the materials used. Many research groups are involved in developing new electrode and electrolyte materials to enhance the overall performance efficiency of the battery. Currently explored electrolytes for Li ion battery applications are in liquid or gel form, which makes well-defined sealing essential. The use of solid electrolytes eliminates the need for containment of liquid electrolytes, which will certainly simplify the cell design and improve the safety and durability. The other advantages of polymer electrolytes include dimensional stability, safety and the ability to prevent lithium dendrite formation. One of the ultimate aims of the present work is to realize all solid state, flexible and environment friendly Li-ion cells with high specific capacity and excellent cycling stability. Part of the present work is hence focused on identifying good polymer based solid electrolytes essential for realizing all solid state polymer based Li ion cells.The present work is an attempt to study the versatile roles of polyaniline in two different fields of technological applications like nonlinear optics and energy storage. Conducting form of doped PANI films with good extent of crystallinity have been realized using a level surface assisted casting method in addition to the generally employed technique of spin coating. Metal nanoparticles embedded PANI offers a rich source for nonlinear optical studies and hence gold and silver nanoparticles have been used for making the nanocomposites in bulk and thin film forms. These PANI nanocomposites are found to exhibit quite dominant third order optical non-linearity. The highlight of these studies is the observation of the interesting phenomenon of the switching between saturable absorption (SA) and reverse saturable absorption (RSA) in the films of Ag/PANI and Au/PANI nanocomposites, which offers prospects of applications in optical switching. The investigations on the energy storage prospects of PANI were carried out on Li enriched PANI which was used as the cathode active material for assembling rechargeable Li-ion cells. For Li enrichment or Li doping of PANI, n-Butyllithium (n-BuLi) in hexanes was used. The Li doping as well as the Li-ion cell assembling were carried out in an argon filled glove box. Coin cells were assembled with Li doped PANI with different doping concentrations, as the cathode, LiPF6 as the electrolyte and Li metal as the anode. These coin cells are found to show reasonably good specific capacity around 22mAh/g and excellent cycling stability and coulombic efficiency around 99%. To improve the specific capacity, composites of Li doped PANI with inorganic cathode active materials like LiFePO4 and LiMn2O4 were synthesized and coin cells were assembled as mentioned earlier to assess the electrochemical capability. The cells assembled using the composite cathodes are found to show significant enhancement in specific capacity to around 40mAh/g. One of the other interesting observations is the complete blocking of the adverse effects of Jahn-Teller distortion, when the composite cathode, PANI-LiMn2O4 is used for assembling the Li-ion cells. This distortion is generally observed, near room temperature, when LiMn2O4 is used as the cathode, which significantly reduces the cycling stability of the cells.

The impact of location and type on the performance of Low-Voltage network connected Battery Energy Storage Systems

This paper assesses the impact of the location and configuration of Battery Energy Storage Systems (BESS) on Low-Voltage (LV) feeders. BESS are now being deployed on LV networks by Distribution Network Operators (DNOs) as an alternative to conventional reinforcement (e.g. upgrading cables and transformers) in response to increased electricity demand from new technologies such as electric vehicles. By storing energy during periods of low demand and then releasing that energy at times of high demand, the peak demand of a given LV substation on the grid can be reduced therefore mitigating or at least delaying the need for replacement and upgrade. However, existing research into this application of BESS tends to evaluate the aggregated impact of such systems at the substation level and does not systematically consider the impact of the location and configuration of BESS on the voltage profiles, losses and utilisation within a given feeder. In this paper, four configurations of BESS are considered: single-phase, unlinked three-phase, linked three-phase without storage for phase-balancing only, and linked three-phase with storage. These four configurations are then assessed based on models of two real LV networks. In each case, the impact of the BESS is systematically evaluated at every node in the LV network using Matlab linked with OpenDSS. The location and configuration of a BESS is shown to be critical when seeking the best overall network impact or when considering specific impacts on voltage, losses, or utilisation separately. Furthermore, the paper also demonstrates that phase-balancing without energy storage can provide much of the gains on unbalanced networks compared to systems with energy storage.

Optimal power management strategy for energy storage with stochastic loads

In this paper, a power management strategy (PMS) has been developed for the control of energy storage in a system subjected to loads of random duration. The PMS minimises the costs associated with the energy consumption of specific systems powered by a primary energy source and equipped with energy storage, under the assumption that the statistical distribution of load durations is known. By including the variability of the load in the cost function, it was possible to define the optimality criteria for the power flow of the storage. Numerical calculations have been performed obtaining the control strategies associated with the global minimum in energy costs, for a wide range of initial conditions of the system. The results of the calculations have been tested on a MATLAB/Simulink model of a rubber tyre gantry (RTG) crane equipped with a flywheel energy storage system (FESS) and subjected to a test cycle, which corresponds to the real operation of a crane in the Port of Felixstowe. The results of the model show increased energy savings and reduced peak power demand with respect to existing control strategies, indicating considerable potential savings for port operators in terms of energy and maintenance costs.

Optical energy storage properties of Sr(2)MgSi(2)O(7):Eu(2+),R(3+) persistent luminescence materials

The details of the mechanism of persistent luminescence were probed by investigating the trap level structure of Sr(2)MgSi(2)O(7):Eu(2+),R(3+) materials (R: Y, La-Lu, excluding Pm and Eu) with thermoluminescence (TL) measurements and Density Functional Theory (DFT) calculations. The TL results indicated that the shallowest traps for each Sr(2)MgSi(2)O(7):Eu(2+),R(3+) material above room temperature were always ca. 0.7 eV corresponding to a strong TL maximum at ca. 90 A degrees C. This main trap energy was only slightly modified by the different co-dopants, which, in contrast, had a significant effect on the depths of the deeper traps. The combined results of the trap level energies obtained from the experimental data and DFT calculations suggest that the main trap responsible for the persistent luminescence of the Sr(2)MgSi(2)O(7):Eu(2+),R(3+) materials is created by charge compensation lattice defects, identified tentatively as oxygen vacancies, induced by the R(3+) co-dopants.

Energy Storage for a Grid-Connected PV-System: A Feasibility Study

The work presented in this thesis concerns the dimensioning of an Energy Storage System (ESS) which will be used as an energy buffer for a grid-connected PV plant. This ESS should help managing the PV plant to inject electricity into the grid according to the requirements of the grid System Operator. It is desired to obtain a final production not below 1300kWh/kWp with a maximum ESS budget of 0.9€/Wp. The PV plant will be sited in Martinique Island and connected to the main grid. This grid is a small one where the perturbations due clouds in the PV generation are not negligible anymore. A software simulation tool, incorporating a model for the PV-plant production, the ESS and the required injection pattern of electricity into the grid has been developed in MS Excel. This tool has been used to optimize the relevant parameters defining the ESS so that the feed-in of electricity into the grid can be controlled to fulfill the conditions given by the System Operator. The inputs used for this simulation tool are, besides the conditions given by the System Operator on the allowed injection pattern, the production data from a similar PV-plant in a close-by location, and variables for defining the ESS. The PV production data used is from a site with similar climate and weather conditions as for the site on the Martinique Island and hence gives information on the short term insolation variations as well as expected annual electricity production. The ESS capacity and the injected electric energy will be the main figures to compare while doing an economic study of the whole plant. Hence, the Net Present Value, Benefit to Cost method and Pay-back period studies are carried on as dependent of the ESS capacity. The conclusion of this work is that it is possible to obtain the requested injection pattern by using an ESS. The design of the ESS can be made within an acceptable budget. The capacity of ESS to link with the PV system depends on the priorities of the final output characteristics, and it also depends on which economic parameter that is chosen as a priority.

Energy Efficiency through Thermal Energy Storage - Evaluation of the Possibilities for the Swedish Building Stock, Phase 1

As a first step in assessing the potential of thermal energy storage in Swedish buildings, the current situation of the Swedish building stock and different storage methods are discussed in this paper. Overall, many buildings are from the 1960’s or earlier having a relatively high energy demand, creating opportunities for large energy savings. The major means of heating are electricity for detached houses and district heating for multi dwelling houses and premises. Cooling needs are relatively low but steadily increasing, emphasizing the need to consider energy storage for both heat and cold. The thermal mass of a building is important for passive storage of thermal energy but this has not been considered much when constructing buildings in Sweden. Instead, common ways of storing thermal energy in Swedish buildings today is in water storage tanks or in the ground using boreholes, while latent thermal energy storage is still very uncommon.

New concepts of the power received by ideal energy storage elements: the instantaneous complex power approach

This paper presents some definitions and concepts of the Instantaneous Complex Power Theory [1] which is a new approach for the Akagi's Instantaneous Reactive Power Theory [2].The powers received by an ideal inductor are interpreted and the knowledge of the actual nature of these powers may lead to changes of the conventional electrical power concepts.

Improved low-voltage-ride-through capability of fixed-speed wind turbines using decentralised control of STATCOM with energy storage system

The design and implementation of a new control scheme for reactive power compensation, voltage regulation and transient stability enhancement for wind turbines equipped with fixed-speed induction generators (IGs) in large interconnected power systems is presented in this study. The low-voltage-ride-through (LVRT) capability is provided by extending the range of the operation of the controlled system to include typical post-fault conditions. A systematic procedure is proposed to design decentralised multi-variable controllers for large interconnected power systems using the linear quadratic (LQ) output-feedback control design method and the controller design procedure is formulated as an optimisation problem involving rank-constrained linear matrix inequality (LMI). In this study, it is shown that a static synchronous compensator (STATCOM) with energy storage system (ESS), controlled via robust control technique, is an effective device for improving the LVRT capability of fixed-speed wind turbines.

Design of alternative energy storage systems for hybrid vehicles based on statistical processing of driving cycles information

Hybrid vehicles represent the future for automakers, since they allow to improve the fuel economy and to reduce the pollutant emissions. A key component of the hybrid powertrain is the Energy Storage System, that determines the ability of the vehicle to store and reuse energy. Though electrified Energy Storage Systems (ESS), based on batteries and ultracapacitors, are a proven technology, Alternative Energy Storage Systems (AESS), based on mechanical, hydraulic and pneumatic devices, are gaining interest because they give the possibility of realizing low-cost mild-hybrid vehicles. Currently, most literature of design methodologies focuses on electric ESS, which are not suitable for AESS design. In this contest, The Ohio State University has developed an Alternative Energy Storage System design methodology. This work focuses on the development of driving cycle analysis methodology that is a key component of Alternative Energy Storage System design procedure. The proposed methodology is based on a statistical approach to analyzing driving schedules that represent the vehicle typical use. Driving data are broken up into power events sequence, namely traction and braking events, and for each of them, energy-related and dynamic metrics are calculated. By means of a clustering process and statistical synthesis methods, statistically-relevant metrics are determined. These metrics define cycle representative braking events. By using these events as inputs for the Alternative Energy Storage System design methodology, different system designs are obtained. Each of them is characterized by attributes, namely system volume and weight. In the last part the work, the designs are evaluated in simulation by introducing and calculating a metric related to the energy conversion efficiency. Finally, the designs are compared accounting for attributes and efficiency values. In order to automate the driving data extraction and synthesis process, a specific script Matlab based has been developed. Results show that the driving cycle analysis methodology, based on the statistical approach, allows to extract and synthesize cycle representative data. The designs based on cycle statistically-relevant metrics are properly sized and have satisfying efficiency values with respect to the expectations. An exception is the design based on the cycle worst-case scenario, corresponding to same approach adopted by the conventional electric ESS design methodologies. In this case, a heavy system with poor efficiency is produced. The proposed new methodology seems to be a valid and consistent support for Alternative Energy Storage System design.

Chemical exfoliation of graphene and its application in organic electronics and energy storage devices

Graphene, the thinnest two-dimensional material possible, is considered as a realistic candidate for the numerous applications in electronic, energy storage and conversion devices due to its unique properties, such as high optical transmittance, high conductivity, excellent chemical and thermal stability. However, the electronic and chemical properties of graphene are highly dependent on their preparation methods. Therefore, the development of novel chemical exfoliation process which aims at high yield synthesis of high quality graphene while maintaining good solution processability is of great concern. This thesis focuses on the solution production of high-quality graphene by wet-chemical exfoliation methods and addresses the applications of the chemically exfoliated graphene in organic electronics and energy storage devices.rnPlatinum is the most commonly used catalysts for fuel cells but they suffered from sluggish electron transfer kinetics. On the other hand, heteroatom doped graphene is known to enhance not only electrical conductivity but also long term operation stability. In this regard, a simple synthetic method is developed for the nitrogen doped graphene (NG) preparation. Moreover, iron (Fe) can be incorporated into the synthetic process. As-prepared NG with and without Fe shows excellent catalytic activity and stability compared to that of Pt based catalysts.rnHigh electrical conductivity is one of the most important requirements for the application of graphene in electronic devices. Therefore, for the fabrication of electrically conductive graphene films, a novel methane plasma assisted reduction of GO is developed. The high electrical conductivity of plasma reduced GO films revealed an excellent electrochemical performance in terms of high power and energy densities when used as an electrode in the micro-supercapacitors.rnAlthough, GO can be prepared in bulk scale, large amount of defect density and low electrical conductivity are major drawbacks. To overcome the intrinsic limitation of poor quality of GO and/or reduced GO, a novel protocol is extablished for mass production of high-quality graphene by means of electrochemical exfoliation of graphite. The prepared graphene shows high electrical conductivity, low defect density and good solution processability. Furthermore, when used as electrodes in organic field-effect transistors and/or in supercapacitors, the electrochemically exfoliated graphene shows excellent device performances. The low cost and environment friendly production of such high-quality graphene is of great importance for future generation electronics and energy storage devices. rn

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.

Application and optimization of a thermal energy storage on a cruise ship

The thesis, developed in collaboration between the team Systems and Equipment for Energy and Environment of Bologna University and Chalmers University of Technology in Goteborg, aims to study the benefits resulting from the adoption of a thermal storage system for marine application. To that purpose a chruis ship has been considered. To reach the purpose has been used the software EGO (Energy Greed Optimization) developed by University of Bologna.

Thermal Energy Storage for Solar Power Production

Solar energy is the most abundant persistent energy resource. It is also an intermittent one available for only a fraction of each day while the demand for electric power never ceases. To produce a significant amount of power at the utility scale, electricity generated from solar energy must be dispatchable and able to be supplied in response to variations in demand. This requires energy storage that serves to decouple the intermittent solar resource from the load and enables around-the-clock power production from solar energy. Practically, solar energy storage technologies must be efficient as any energy loss results in an increase in the amount of required collection hardware, the largest cost in a solar electric power system. Storing solar energy as heat has been shown to be an efficient, scalable, and relatively low-cost approach to providing dispatchable solar electricity. Concentrating solar power systems that include thermal energy storage (TES) use mirrors to focus sunlight onto a heat exchanger where it is converted to thermal energy that is carried away by a heat transfer fluid and used to drive a conventional thermal power cycle (e.g., steam power plant), or stored for later use. Several approaches to TES have been developed and can generally be categorized as either thermophysical (wherein energy is stored in a hot fluid or solid medium or by causing a phase change that can later be reversed to release heat) or thermochemical (in which energy is stored in chemical bonds requiring two or more reversible chemical reactions).

Computational simulations of latent heat thermal energy storage systems - with innovative and first-principles based simulation for the underlying unsteady melting (and solidification) processes

This thesis develops an effective modeling and simulation procedure for a specific thermal energy storage system commonly used and recommended for various applications (such as an auxiliary energy storage system for solar heating based Rankine cycle power plant). This thermal energy storage system transfers heat from a hot fluid (termed as heat transfer fluid - HTF) flowing in a tube to the surrounding phase change material (PCM). Through unsteady melting or freezing process, the PCM absorbs or releases thermal energy in the form of latent heat. Both scientific and engineering information is obtained by the proposed first-principle based modeling and simulation procedure. On the scientific side, the approach accurately tracks the moving melt-front (modeled as a sharp liquid-solid interface) and provides all necessary information about the time-varying heat-flow rates, temperature profiles, stored thermal energy, etc. On the engineering side, the proposed approach is unique in its ability to accurately solve – both individually and collectively – all the conjugate unsteady heat transfer problems for each of the components of the thermal storage system. This yields critical system level information on the various time-varying effectiveness and efficiency parameters for the thermal storage system.

Domestic hot water consumption vs. solar thermal energy storage: the optimum size of the storage tank

Many efforts have been made in order to adequate the production of a solar thermal collector field to the consumption of domestic hot water of the inhabitants of a building. In that sense, much has been achieved in different domains: research agencies, government policies and manufacturers. However, most of the design rules of the solar plants are based on steady state models, whereas solar irradiance, consumption and thermal accumulation are inherently transient processes. As a result of this lack of physical accuracy, thermal storage tanks are sometimes left to be as large as the designer decides without any aforementioned precise recommendation. This can be a problem if solar thermal systems are meant to be implemented in nowadays buildings, where there is a shortage of space. In addition to that, an excessive storage volume could not result more efficient in many residential applications, but costly, extreme in space consumption and in some cases too heavy. A proprietary transient simulation program has been developed and validated with a detailed measurement campaign in an experimental facility. In situ environmental data have been obtained through a whole year of operation. They have been gathered at intervals of 10 min for a solar plant of 50 m2 with a storage tank of 3 m3, including the equipment for domestic hot water production of a typical apartment building. This program has been used to obtain the design and dimensioning criteria of DHW solar plants under daily transient conditions throughout a year and more specifically the size of the storage tank for a multi storey apartment building. Comparison of the simulation results with the current Spanish regulation applicable, “Código Técnico de la Edificación” (CTE 2006), offers fruitful details and establishes solar facilities dimensioning criteria.