Carbon nanotube based systems for high energy efficient applications

In the current age of fast-depleting conventional energy sources, top priority is given to exploring non-conventional energy sources, designing highly efficient energy storage systems and converting existing machines/instruments/devices into energy-efficient ones. ‘Energy efficiency’ is one of the important challenges for today’s scientific and research community, worldwide. In line with this demand, the current research was focused on developing two highly energy-efficient devices – field emitters and Li-ion batteries, using beneficial properties of carbon nanotubes (CNT). Interface-engineered, directly grown CNTs were used as cathode in field emitters, while similar structure was applied as anode in Li-ion batteries. Interface engineering was found to offer minimum resistance to electron flow and strong bonding with the substrate. Both field emitters and Li-ion battery anodes were benefitted from these advantages, demonstrating high energy efficiency. Field emitter, developed during this research, could be characterized by low turn-on field, high emission current, very high field enhancement factor and extremely good stability during long-run. Further, application of 3-dimensional design to these field emitters resulted in achieving one of the highest emission current densities reported so far. The 3-D field emitter registered 27 times increase in current density, as compared to their 2-D counterparts. These achievements were further followed by adding new functionalities, transparency and flexibility, to field emitters, keeping in view of current demand for flexible displays. A CNT-graphene hybrid structure showed appreciable emission, along with very good transparency and flexibility. Li-ion battery anodes, prepared using the interface-engineered CNTs, have offered 140% increment in capacity, as compared to conventional graphite anodes. Further, it has shown very good rate capability and an exceptional ‘zero capacity degradation’ during long cycle operation. Enhanced safety and charge transfer mechanism of this novel anode structure could be explained from structural characterization. In an attempt to progress further, CNTs were coated with ultrathin alumina by atomic layer deposition technique. These alumina-coated CNT anodes offered much higher capacity and an exceptional rate capability, with very low capacity degradation in higher current densities. These highly energy efficient CNT based anodes are expected to enhance capacities of future Li-ion batteries.

XML storage and retrieval using the semantic binary object -oriented database system (SEM-ODB)

Over the past five years, XML has been embraced by both the research and industrial community due to its promising prospects as a new data representation and exchange format on the Internet. The widespread popularity of XML creates an increasing need to store XML data in persistent storage systems and to enable sophisticated XML queries over the data. The currently available approaches to addressing the XML storage and retrieval issue have the limitations of either being not mature enough (e.g. native approaches) or causing inflexibility, a lot of fragmentation and excessive join operations (e.g. non-native approaches such as the relational database approach). ^ In this dissertation, I studied the issue of storing and retrieving XML data using the Semantic Binary Object-Oriented Database System (Sem-ODB) to leverage the advanced Sem-ODB technology with the emerging XML data model. First, a meta-schema based approach was implemented to address the data model mismatch issue that is inherent in the non-native approaches. The meta-schema based approach captures the meta-data of both Document Type Definitions (DTDs) and Sem-ODB Semantic Schemas, thus enables a dynamic and flexible mapping scheme. Second, a formal framework was presented to ensure precise and concise mappings. In this framework, both schemas and the conversions between them are formally defined and described. Third, after major features of an XML query language, XQuery, were analyzed, a high-level XQuery to Semantic SQL (Sem-SQL) query translation scheme was described. This translation scheme takes advantage of the navigation-oriented query paradigm of the Sem-SQL, thus avoids the excessive join problem of relational approaches. Finally, the modeling capability of the Semantic Binary Object-Oriented Data Model (Sem-ODM) was explored from the perspective of conceptually modeling an XML Schema using a Semantic Schema. ^ It was revealed that the advanced features of the Sem-ODB, such as multi-valued attributes, surrogates, the navigation-oriented query paradigm, among others, are indeed beneficial in coping with the XML storage and retrieval issue using a non-XML approach. Furthermore, extensions to the Sem-ODB to make it work more effectively with XML data were also proposed. ^

Improving Storage Performance Through Layout Optimizations

Disk drives are the bottleneck in the processing of large amounts of data used in almost all common applications. File systems attempt to reduce this by storing data sequentially on the disk drives, thereby reducing the access latencies. Although this strategy is useful when data is retrieved sequentially, the access patterns in real world workloads is not necessarily sequential and this mismatch results in storage I/O performance degradation. This thesis demonstrates that one way to improve the storage performance is to reorganize data on disk drives in the same way in which it is mostly accessed. We identify two classes of accesses: static, where access patterns do not change over the lifetime of the data and dynamic, where access patterns frequently change over short durations of time, and propose, implement and evaluate layout strategies for each of these. Our strategies are implemented in a way that they can be seamlessly integrated or removed from the system as desired. We evaluate our layout strategies for static policies using tree-structured XML data where accesses to the storage device are mostly of two kinds - parent-tochild or child-to-sibling. Our results show that for a specific class of deep-focused queries, the existing file system layout policy performs better by 5-54X. For the non-deep-focused queries, our native layout mechanism shows an improvement of 3-127X. To improve performance of the dynamic access patterns, we implement a self-optimizing storage system that performs rearranges popular block accesses on a dedicated partition based on the observed workload characteristics. Our evaluation shows an improvement of over 80% in the disk busy times over a range of workloads. These results show that applying the knowledge of data access patterns for allocation decisions can substantially improve the I/O performance.

Efficient Storage and Domain-Specific Information Discovery on Semistructured Documents

The increasing amount of available semistructured data demands efficient mechanisms to store, process, and search an enormous corpus of data to encourage its global adoption. Current techniques to store semistructured documents either map them to relational databases, or use a combination of flat files and indexes. These two approaches result in a mismatch between the tree-structure of semistructured data and the access characteristics of the underlying storage devices. Furthermore, the inefficiency of XML parsing methods has slowed down the large-scale adoption of XML into actual system implementations. The recent development of lazy parsing techniques is a major step towards improving this situation, but lazy parsers still have significant drawbacks that undermine the massive adoption of XML. Once the processing (storage and parsing) issues for semistructured data have been addressed, another key challenge to leverage semistructured data is to perform effective information discovery on such data. Previous works have addressed this problem in a generic (i.e. domain independent) way, but this process can be improved if knowledge about the specific domain is taken into consideration. This dissertation had two general goals: The first goal was to devise novel techniques to efficiently store and process semistructured documents. This goal had two specific aims: We proposed a method for storing semistructured documents that maps the physical characteristics of the documents to the geometrical layout of hard drives. We developed a Double-Lazy Parser for semistructured documents which introduces lazy behavior in both the pre-parsing and progressive parsing phases of the standard Document Object Model's parsing mechanism. The second goal was to construct a user-friendly and efficient engine for performing Information Discovery over domain-specific semistructured documents. This goal also had two aims: We presented a framework that exploits the domain-specific knowledge to improve the quality of the information discovery process by incorporating domain ontologies. We also proposed meaningful evaluation metrics to compare the results of search systems over semistructured documents.

Structure, Morphology, and Electrochemical Properties of Transition Metal Oxide, Hydroxide, and Phosphate Nanomaterials for Energy Storage

Energy storage technologies are crucial for efficient utilization of electricity. Supercapacitors and rechargeable batteries are of currently available energy storage systems. Transition metal oxides, hydroxides, and phosphates are the most intensely investigated electrode materials for supercapacitors and rechargeable batteries due to their high theoretical charge storage capacities resulted from reversible electrochemical reactions. Their insulating nature, however, causes sluggish electron transport kinetics within these electrode materials, hindering them from reaching the theoretical maximum. The conductivity of these transition metal based-electrode materials can be improved through three main approaches; nanostructuring, chemical substitution, and introducing carbon matrices. These approaches often lead to unique electrochemical properties when combined and balanced.

Ethanol-mediated solvothermal synthesis we developed is found to be highly effective for controlling size and morphology of transition metal-based electrode materials for both pseudocapacitors and batteries. The morphology and the degree of crystallinity of nickel hydroxide are systematically changed by adding various amounts glucose to the solvothermal synthesis. Nickel hydroxide produced in this manner exhibited increased pseudocapacitance, which is partially attributed to the increased surface area. Interestingly, this morphology effect on cobalt doped-nickel hydroxide is found to be more effective at low cobalt contents than at high cobalt contents in terms of improving the electrochemical performance.

Moreover, a thin layer of densely packed nickel oxide flakes on carbon paper substrate was successfully prepared via the glucose-assisted solvothermal synthesis, resulting in the improved electrode conductivity. When reduced graphene oxide was used for conductive coating on as-prepared nickel oxide electrode, the electrode conductivity was only slightly improved. This finding reveals that the influence of reduced graphene oxide coating, increasing the electrode conductivity, is not that obvious when the electrode is already highly conductive to begin with.

We were able to successfully control the interlayer spacing and reduce the particle size of layered titanium hydrogeno phosphate material using our ethanol-mediated solvothermal reaction. In layered structure, interlayer spacing is the key parameter for fast ion diffusion kinetics. The nanosized layered structure prepared via our method, however, exhibited high sodium-ion storage capacity regardless of the interlayer spacing, implying that interlayer space may not be the primary factor for sodium-ion diffusion in nanostructured materials, where many interstitials are available for sodium-ion diffusion.

Our ethanol-mediated solvothermal reaction was also effective for synthesis of NaTi2(PO4)3 nanoparticles with uniform size and morphology, well connected by a carbon nanotube network. This composite electrode exhibited high capacity, which is comparable to that in aqueous electrolyte, probably due to the uniform morphology and size where the preferable surface for sodium-ion diffusion is always available in all individual particles.

Fundamental understandings of the relationship between electrode microstructures and electrochemical properties discussed in this dissertation will be important to design high performance energy storage system applications.

Local Storage Meets Local Demand: A Technical Solution to Future Power Distribution System

Future power systems are expected to integrate large-scale stochastic and intermittent generation and load due to reduced use of fossil fuel resources, including renewable energy sources (RES) and electric vehicles (EV). Inclusion of such resources poses challenges for the dynamic stability of synchronous transmission and distribution networks, not least in terms of generation where system inertia may not be wholly governed by large-scale generation but displaced by small-scale and localised generation. Energy storage systems (ESS) can limit the impact of dispersed and distributed generation by offering supporting reserve while accommodating large-scale EV connection; the latter (load) also participating in storage provision. In this paper, a local energy storage system (LESS) is proposed. The structure, requirement and optimal sizing of the LESS are discussed. Three operating modes are detailed, including: 1) storage pack management; 2) normal operation; and 3) contingency operation. The proposed LESS scheme is evaluated using simulation studies based on data obtained from the Northern Ireland regional and residential network.

Nano-Engineering of Densely Packed Electrochemical Energy Storage Architectures by Atomic Layer Deposition

Nanostructures are highly attractive for future electrical energy storage devices because they enable large surface area and short ion transport time through thin electrode layers for high power devices. Significant enhancement in power density of batteries has been achieved by nano-engineered structures, particularly anode and cathode nanostructures spatially separated far apart by a porous membrane and/or a defined electrolyte region. A self-aligned nanostructured battery fully confined within a single nanopore presents a powerful platform to determine the rate performance and cyclability limits of nanostructured storage devices. Atomic layer deposition (ALD) has enabled us to create and evaluate such structures, comprised of nanotubular electrodes and electrolyte confined within anodic aluminum oxide (AAO) nanopores. The V2O5- V2O5 symmetric nanopore battery displays exceptional power-energy performance and cyclability when tested as a massively parallel device (~2billion/cm2), each with ~1m3 volume (~1fL). Cycled between 0.2V and 1.8V, this full cell has capacity retention of 95% at 5C rate and 46% at 150C, with more than 1000 charge/discharge cycles. These results demonstrate the promise of ultrasmall, self-aligned/regular, densely packed nanobattery structures as a testbed to study ionics and electrodics at the nanoscale with various geometrical modifications and as a building block for high performance energy storage systems[1, 2]. Further increase of full cell output potential is also demonstrated in asymmetric full cell configurations with various low voltage anode materials. The asymmetric full cell nanopore batteries, comprised of V2O5 as cathode and prelithiated SnO2 or anatase phase TiO2 as anode, with integrated nanotubular metal current collectors underneath each nanotubular storage electrode, also enabled by ALD. By controlling the amount of lithium ion prelithiated into SnO2 anode, we can tune full cell output voltage in the range of 0.3V and 3V. This asymmetric nanopore battery array displays exceptional rate performance and cyclability. When cycled between 1V and 3V, it has capacity retention of approximately 73% at 200C rate compared to 1C, with only 2% capacity loss after more than 500 charge/discharge cycles. With increased full cell output potential, the asymmetric V2O5-SnO2 nanopore battery shows significantly improved energy and power density. This configuration presents a more realistic test - through its asymmetric (vs symmetric) configuration – of performance and cyclability in nanoconfined environment. This dissertation covers (1) Ultra small electrochemical storage platform design and fabrication, (2) Electron and ion transport in nanostructured electrodes inside a half cell configuration, (3) Ion transport between anode and cathode in confined nanochannels in symmetric full cells, (4) Scale up energy and power density with geometry optimization and low voltage anode materials in asymmetric full cell configurations. As a supplement, selective growth of ALD to improve graphene conductance will also be discussed[3]. References: 1. Liu, C., et al., (Invited) A Rational Design for Batteries at Nanoscale by Atomic Layer Deposition. ECS Transactions, 2015. 69(7): p. 23-30. 2. Liu, C.Y., et al., An all-in-one nanopore battery array. Nature Nanotechnology, 2014. 9(12): p. 1031-1039. 3. Liu, C., et al., Improving Graphene Conductivity through Selective Atomic Layer Deposition. ECS Transactions, 2015. 69(7): p. 133-138.

Modeling of Electric Hybrid Vehicles based on Innovative Energy Storage Technologies for Super Sports Cars Applications

Today, the contribution of the transportation sector on greenhouse gases is evident. The fast consumption of fossil fuels and its impact on the environment has given a strong impetus to the development of vehicles with better fuel economy. Hybrid electric vehicles fit into this context with different targets, starting from the reduction of emissions and fuel consumption, but also for performance and comfort enhancement. Vehicles exist with various missions; super sport cars usually aim to reach peak performance and to guarantee a great driving experience to the driver, but great attention must also be paid to fuel consumption. According to the vehicle mission, hybrid vehicles can differ in the powertrain configuration and the choice of the energy storage system. Lamborghini has recently invested in the development of hybrid super sport cars, due to performance and comfort reasons, with the possibility to reduce fuel consumption. This research activity has been conducted as a joint collaboration between the University of Bologna and the sportscar manufacturer, to analyze the impact of innovative energy storage solutions on the hybrid vehicle performance. Capacitors have been studied and modeled to analyze the pros and cons of such solution with respect to batteries. To this aim, a full simulation environment has been developed and validated to provide a concept design tool capable of precise results and able to foresee the longitudinal performance on regulated emission cycles and real driving conditions, with a focus on fuel consumption. In addition, the target of the research activity is to deepen the study of hybrid electric super sports cars in the concept development phase, focusing on defining the control strategies and the energy storage system’s technology that best suits the needs of the vehicles. This dissertation covers the key steps that have been carried out in the research project.

Strategies for lowering the environmental impact of different electrochemical energy storage system

The continuous growth of global population brings an exponential increase on energy consumption and greenhouse gas emission in the atmosphere contributing to the increase of the planet temperature. Therefore, it is mandatory to adopt renewable energy production systems like photovoltaic or wind power: unfortunately, the main limit of these technologies is the natural intermittence of the energy sources that limits their applicability. The key enabling technology for a widespread usage of clean power sources are electrochemical energy storage systems, most commonly known as batteries. Batteries will enable the storage of energy during overproduction period and the release during low production period stabilizing the power outcome, allowing the connection to the main grid and increasing the applicability of renewable energy sources. Despite the high number of benefits that the widespread use of batteries will bring, starting from the reduction of CO2 emitted in the atmosphere, it is necessary also to take care of the environmental impact of processes and materials used for the production of electrochemical storage systems. In addition, there are many different battery systems, with different chemistries and designs that require specific strategies. Nowadays, the most part of the materials and chemicals used for battery production are toxic for humans and the environment. For this reason, this Ph.D. thesis addresses the challenging scope of lowering the environmental impact of manufacturing processes of different electrochemical energy storage systems using natural derived or low carbon footprint materials while increasing the performances with respect to commercial devices. The activities carried out during my Ph.D. cover a high number of different electrochemical storage systems involving a wide range of electrochemical processes from capacitive to faradic. New materials, different production processes and new battery design, all in view of sustainability and low environmental impact, increased the innovative and challenging aspects of this work.

Study of materials and interphases for electrochemical energy storage from renewable sources

Batteries should be refined depending on their application for a future in which the sustainable energy demand increases. On the one hand, it is fundamental to improve their safety, prevent failures, increase energy density, and reduce production costs. On the other hand, new battery materials and architecture are required to satisfy the growing demand. This thesis explores different electrochemical energy storage systems and new methodologies to investigate complex and dynamic processes. Lithium-ion batteries are described in all their cell components. In these systems, this thesis investigates negative electrodes. Both the development of new sustainable materials and new in situ electrode characterization methods were explored. One strategy to achieve high-energy systems is employing lithium metal anodes. In this framework, ammonium hexafluorophosphate is demonstrated to be a suitable additive for stabilizing the interphase and preventing uncontrolled dendritic deposition. Deposition/stripping cycles, electrochemical impedance spectroscopy, in situ optical microscopy, and operando confocal Raman spectroscopy have been used to study lithium metal-electrolyte interphase in the presence of the additive. Redox Flow Batteries (RFBs) are proposed as a sustainable alternative for stationary applications. An all-copper aqueous RFB (CuRFB) has been studied in all its aspects. For the electrolyte optimization, spectro-electrochemical tests in diluted solution have been used to get information on the electrolyte’s electrochemical behaviour with different copper complexes distributions. In concentrated solutions, the effects of copper-to-ligand ratios, the concentration, and the counter-ion of the complexing agent were evaluated. Electrode thermal treatment was optimized, finding a compromise between the electrochemical performance and the carbon footprint. On the membrane side, a new method for permeability studies was designed using scanning electrochemical microscopy (SECM). The Cu(II) permeability of several membranes was tested, obtaining direct visualization of Cu(II) concentration in space. Also, two spectrophotometric approaches were designed for SoC monitoring systems for negative and positive half-cells.

Power flow forecasting and smart charging for electric vehicle charging systems with photovoltaic integration

An essential role in the global energy transition is attributed to Electric Vehicles (EVs) the energy for EV traction can be generated by renewable energy sources (RES), also at a local level through distributed power plants, such as photovoltaic (PV) systems. However, EV integration with electrical systems might not be straightforward. The intermittent RES, combined with the high and uncontrolled aggregate EV charging, require an evolution toward new planning and paradigms of energy systems. In this context, this work aims to provide a practical solution for EV charging integration in electrical systems with RES. A method for predicting the power required by an EV fleet at the charging hub (CH) is developed in this thesis. The proposed forecasting method considers the main parameters on which charging demand depends. The results of the EV charging forecasting method are deeply analyzed under different scenarios. To reduce the EV load intermittency, methods for managing the charging power of EVs are proposed. The main target was to provide Charging Management Systems (CMS) that modulate EV charging to optimize specific performance indicators such as system self-consumption, peak load reduction, and PV exploitation. Controlling the EV charging power to achieve specific optimization goals is also known as Smart Charging (SC). The proposed techniques are applied to real-world scenarios demonstrating performance improvements in using SC strategies. A viable alternative to maximize integration with intermittent RES generation is the integration of energy storage. Battery Energy Storage Systems (BESS) may be a buffer between peak load and RES production. A sizing algorithm for PV+BESS integration in EV charging hubs is provided. The sizing optimization aims to optimize the system's energy and economic performance. The results provide an overview of the optimal size that the PV+BESS plant should have to improve whole system performance in different scenarios.

Intelligent management of end consumers loads including electric vehicles through a SCADA system

The large penetration of intermittent resources, such as solar and wind generation, involves the use of storage systems in order to improve power system operation. Electric Vehicles (EVs) with gridable capability (V2G) can operate as a means for storing energy. This paper proposes an algorithm to be included in a SCADA (Supervisory Control and Data Acquisition) system, which performs an intelligent management of three types of consumers: domestic, commercial and industrial, that includes the joint management of loads and the charge/discharge of EVs batteries. The proposed methodology has been implemented in a SCADA system developed by the authors of this paper – the SCADA House Intelligent Management (SHIM). Any event in the system, such as a Demand Response (DR) event, triggers the use of an optimization algorithm that performs the optimal energy resources scheduling (including loads and EVs), taking into account the priorities of each load defined by the installation users. A case study considering a specific consumer with several loads and EVs is presented in this paper.

Distributed energy resource short-term scheduling using signaled particle swarm optimization

Distributed Energy Resources (DER) scheduling in smart grids presents a new challenge to system operators. The increase of new resources, such as storage systems and demand response programs, results in additional computational efforts for optimization problems. On the other hand, since natural resources, such as wind and sun, can only be precisely forecasted with small anticipation, short-term scheduling is especially relevant requiring a very good performance on large dimension problems. Traditional techniques such as Mixed-Integer Non-Linear Programming (MINLP) do not cope well with large scale problems. This type of problems can be appropriately addressed by metaheuristics approaches. This paper proposes a new methodology called Signaled Particle Swarm Optimization (SiPSO) to address the energy resources management problem in the scope of smart grids, with intensive use of DER. The proposed methodology’s performance is illustrated by a case study with 99 distributed generators, 208 loads, and 27 storage units. The results are compared with those obtained in other methodologies, namely MINLP, Genetic Algorithm, original Particle Swarm Optimization (PSO), Evolutionary PSO, and New PSO. SiPSO performance is superior to the other tested PSO variants, demonstrating its adequacy to solve large dimension problems which require a decision in a short period of time.

An integrated approach for distributed energy resource short term scheduling in smart grids considering realistic power system simulation

The large increase of distributed energy resources, including distributed generation, storage systems and demand response, especially in distribution networks, makes the management of the available resources a more complex and crucial process. With wind based generation gaining relevance, in terms of the generation mix, the fact that wind forecasting accuracy rapidly drops with the increase of the forecast anticipation time requires to undertake short-term and very short-term re-scheduling so the final implemented solution enables the lowest possible operation costs. This paper proposes a methodology for energy resource scheduling in smart grids, considering day ahead, hour ahead and five minutes ahead scheduling. The short-term scheduling, undertaken five minutes ahead, takes advantage of the high accuracy of the very-short term wind forecasting providing the user with more efficient scheduling solutions. The proposed method uses a Genetic Algorithm based approach for optimization that is able to cope with the hard execution time constraint of short-term scheduling. Realistic power system simulation, based on PSCAD , is used to validate the obtained solutions. The paper includes a case study with a 33 bus distribution network with high penetration of distributed energy resources implemented in PSCAD .

An optimal scheduling problem in distribution networks considering V2G

This paper addresses the problem of energy resource scheduling. An aggregator will manage all distributed resources connected to its distribution network, including distributed generation based on renewable energy resources, demand response, storage systems, and electrical gridable vehicles. The use of gridable vehicles will have a significant impact on power systems management, especially in distribution networks. Therefore, the inclusion of vehicles in the optimal scheduling problem will be very important in future network management. The proposed particle swarm optimization approach is compared with a reference methodology based on mixed integer non-linear programming, implemented in GAMS, to evaluate the effectiveness of the proposed methodology. The paper includes a case study that consider a 32 bus distribution network with 66 distributed generators, 32 loads and 50 electric vehicles.