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.

Graphene for energy storage

Due to its excellent mechanical, termal, optical and electrical properties, graphene has recently attracted increasing attention. It provides a huge surface area (2630m2 g-1) and high electrical conductivity, making it an attractive material for applications in energy-storage systems.

Towards cheaper, safer and low environmental impact materials for energy storage devices: natural resources-derived carbon based electrodes and aqueous electrolytes for supercapacitors

The growing market of electrical cars, portable electronics, photovoltaic systems..etc. requires the development of efficient, low-cost, and low environmental impact energy storage devices (ESDs) including batteries and supercapacitors.. Due to their extended charge-discharge cycle, high specific capacitance, and power capabilities supercapacitors are considered among the most attractive ESDs. Over the last decade, research and development in supercapacitor technology have accelerated: thousands of articles have been published in the literature describing the electrochemical properties of the electrode materials and electrolyte in addition to separators and current collectors. Carbon-based supercapacitor electrodes materials have gained increasing attention due to their high specific surface area, good electrical conductivity, and excellent stability in harsh environments, as well as other characteristics. Recently, there has been a surge of interest in activated carbon derived from low-cost abundant sources such as biomass for supercapacitor electrode materials. Also, particular attention was given to a major challenging issue concerning the substitution of organic solutions currently used as electrolytes due to their highest electrochemical stability window even though their high cost, toxicity, and flammability. In this regard, the main objective of this thesis is to investigate the performances of supercapacitors using low cost abundant safe, and low environmental impact materials for electrodes and electrolytes. Several prototypes were constructed and tested using natural resources through optimization of the preparation of appropriate carbon electrodes using agriculture by-products waste or coal (i.e. Argan shell or Anthracite from Jerrada). Such electrodes were tested using several electrolyte formulations (aqueous and water in salt electrolytes) beneficing their non-flammability, lower cost, and environmental impact; the characteristics that provide a promising opportunity to design safer, inexpensive, and environmentally friendly devices compared to organic electrolytes.

Predictive Optimal Matrix Converter Control for a Dynamic Voltage Restorer with Flywheel Energy Storage

This paper presents a predictive optimal matrix converter controller for a flywheel energy storage system used as Dynamic Voltage Restorer (DVR). The flywheel energy storage device is based on a steel seamless tube mounted as a vertical axis flywheel to store kinetic energy. The motor/generator is a Permanent Magnet Synchronous Machine driven by the AC-AC Matrix Converter. The matrix control method uses a discrete-time model of the converter system to predict the expected values of the input and output currents for all the 27 possible vectors generated by the matrix converter. An optimal controller minimizes control errors using a weighted cost functional. The flywheel and control process was tested as a DVR to mitigate voltage sags and swells. Simulation results show that the DVR is able to compensate the critical load voltage without delays, voltage undershoots or overshoots, overcoming the input/output coupling of matrix converters.

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.

Control of second-life hybrid battery energy storage system based on modular boost-multilevel buck converter

To fully utilize second-life batteries on the grid system, a hybrid battery scheme needs to be considered for several reasons: the uncertainty over using a single source supply chain for second-life batteries, the differences in evolving battery chemistry and battery configuration by different suppliers to strive for greater power levels, and the uncertainty of degradation within a second-life battery. Therefore, these hybrid battery systems could have widely different module voltage, capacity, and initial state of charge and state of health. In order to suitably integrate and control these widely different batteries, a suitable multimodular converter topology and an associated control structure are required. This paper addresses these issues proposing a modular boost-multilevel buck converter based topology to integrate these hybrid second-life batteries to a grid-tie inverter. Thereafter, a suitable module-based distributed control architecture is introduced to independently utilize each converter module according to its characteristics. The proposed converter and control architecture are found to be flexible enough to integrate widely different batteries to an inverter dc link. Modeling, analysis, and experimental validation are performed on a single-phase modular hybrid battery energy storage system prototype to understand the operation of the control strategy with different hybrid battery configurations.

Second life battery energy storage systems:converter topology and redundancy selection

Battery energy storage systems have traditionally been manufactured using new batteries with a good reliability. The high cost of such a system has led to investigations of using second life transportation batteries to provide an alternative energy storage capability. However, the reliability and performance of these batteries is unclear and multi-modular power electronics with redundancy have been suggested as a means of helping with this issue. This paper reviews work already undertaken on battery failure rate to suggest suitable figures for use in reliability calculations. The paper then uses reliability analysis and a numerical example to investigate six different multi-modular topologies and suggests how the number of series battery strings and power electronic module redundancy should be determined for the lowest hardware cost using a numerical example. The results reveal that the cascaded dc-side modular with single inverter is the lowest cost solution for a range of battery failure rates.

Sizing energy storage on the 11kV distribution network

The cost and limited flexibility of traditional approaches to 11kV network reinforcement threatens to constrain the uptake of low carbon technologies. Ofgem has released £500m of funding for DNOs to trial innovative techniques and share the learning with the rest of the industry. One of the techniques under study is the addition of Energy Storage at key substations to the network to help with peak load lopping. This paper looks in detail at the sizing algorithm for use in the assessment of alternatives to traditional reinforcement and investigates a method of sizing a battery for use on a Network taking into account load growth, capacity fade and battery lifecycle issues. A further complication to the analysis is the method of operation of the battery system and how this affects the Depth of Discharge (DoD). The proposed method is being trialled on an area of 11kV network in Milton Keynes Central area and the simulation results are presented in this paper.

Analysis and design of power management scheme for an on-board solar energy storage system

This paper investigates the power management issues in a mobile solar energy storage system. A multi-converter based energy storage system is proposed, in which solar power is the primary source while the grid or the diesel generator is selected as the secondary source. The existence of the secondary source facilitates the battery state of charge detection by providing a constant battery charging current. Converter modeling, multi-converter control system design, digital implementation and experimental verification are introduced and discussed in details. The prototype experiment indicates that the converter system can provide a constant charging current during solar converter maximum power tracking operation, especially during large solar power output variation, which proves the feasibility of the proposed design. © 2014 IEEE.

Adaptive control of hybrid battery energy storage systems under capacity fade

There is an increasing call for applications which use a mixture of batteries. These hybrid battery solutions may contain different battery types for example; using second life ex-transportation batteries in grid support applications or a combination of high power, low energy and low power, high energy batteries to meet multiple energy requirements or even the same battery types but under different states of health for example, being able to hot swap out a battery when it has failed in an application without changing all the batteries and ending up with batteries with different performances, capacities and impedances. These types of applications typically use multi-modular converters to allow hot swapping to take place without affecting the overall performance of the system. A key element of the control is how the different battery performance characteristics may be taken into account and the how the power is then shared among the different batteries in line with their performance. This paper proposes a control strategy which allows the power in the batteries to be effectively distributed even under capacity fade conditions using adaptive power sharing strategy. This strategy is then validated against a system of three different battery types connected to a multi-modular converter both with and without capacity fade mechanisms in place.

Analysis and comparative study of different converter modes in modular second life hybrid battery energy storage systems

The use of ex-transportation battery system (i.e. second life EV/HEV batteries) in grid applications is an emerging field of study. A hybrid battery scheme offers a more practical approach in second life battery energy storage systems because battery modules could be from different sources/ vehicle manufacturers depending on the second life supply chain and have different characteristics e.g. voltage levels, maximum capacity and also different levels of degradations. Recent research studies have suggested a dc-side modular multilevel converter topology to integrate these hybrid batteries to a grid-tie inverter. Depending on the battery module characteristics, the dc-side modular converter can adopt different modes such as boost, buck or boost-buck to suitably transfer the power from battery to the grid. These modes have different switching techniques, control range, different efficiencies, which give a system designer choice on operational mode. This paper presents an analysis and comparative study of all the modes of the converter along with their switching performances in detail to understand the relative advantages and disadvantages of each mode to help to select the suitable converter mode. Detailed study of all the converter modes and thorough experimental results based on a multi-modular converter prototype based on hybrid batteries has been presented to validate the analysis.

Control of cascaded DC-DC converter based hybrid battery energy storage systems - Part II:Lyapunov approach

A cascaded DC-DC boost converter is one of the ways to integrate hybrid battery types within a grid-tie inverter. Due to the presence of different battery parameters within the system such as, state-of-charge and/or capacity, a module based distributed power sharing strategy may be used. To implement this sharing strategy, the desired control reference for each module voltage/current control loop needs to be dynamically varied according to these battery parameters. This can cause stability problem within the cascaded converters due to relative battery parameter variations when using the conventional PI control approach. This paper proposes a new control method based on Lyapunov Functions to eliminate this issue. The proposed solution provides a global asymptotic stability at a module level avoiding any instability issue due to parameter variations. A detailed analysis and design of the nonlinear control structure are presented under the distributed sharing control. At last thorough experimental investigations are shown to prove the effectiveness of the proposed control under grid-tie conditions.

Control of cascaded DC-DC converter-based hybrid battery energy storage systems - Part I:stability Issue

There is an emerging application which uses a mixture of batteries within an energy storage system. These hybrid battery solutions may contain different battery types. A DC-side cascaded boost converters along with a module based distributed power sharing strategy has been proposed to cope with variations in battery parameters such as, state-of-charge and/or capacity. This power sharing strategy distributes the total power among the different battery modules according to these battery parameters. Each module controller consists of an outer voltage loop with an inner current loop where the desired control reference for each control loop needs to be dynamically varied according to battery parameters to undertake this sharing. As a result, the designed control bandwidth or stability margin of each module control loop may vary in a wide range which can cause a stability problem within the cascaded converter. This paper reports such a unique issue and thoroughly investigates the stability of the modular converter under the distributed sharing scheme. The paper shows that a cascaded PI control loop approach cannot guarantee the system stability throughout the operating conditions. A detailed analysis of the stability issue and the limitations of the conventional approach are highlighted. Finally in-depth experimental results are presented to prove the stability issue using a modular hybrid battery energy storage system prototype under various operating conditions.