Work Extraction and Energy Storage in the Dicke Model

We study work extraction from the Dicke model achieved using simple unitary cyclic transformations keeping into account both a non optimal unitary protocol, and the energetic cost of creating the initial state. By analyzing the role of entanglement, we find that highly entangled states can be inefficient for energy storage when considering the energetic cost of creating the state. Such surprising result holds notwithstanding the fact that the criticality of the model at hand can sensibly improve the extraction of work. While showing the advantages of using a many-body system for work extraction, our results demonstrate that entanglement is not necessarily advantageous for energy storage purposes, when non optimal processes are considered. Our work shows the importance of better understanding the complex interconnections between non-equilibrium thermodynamics of quantum systems and correlations among their subparts.

Application of battery energy storage in the Québec interconnection

Le Système Stockage de l’Énergie par Batterie ou Batterie de Stockage d’Énergie (BSE) offre de formidables atouts dans les domaines de la production, du transport, de la distribution et de la consommation d’énergie électrique. Cette technologie est notamment considérée par plusieurs opérateurs à travers le monde entier, comme un nouveau dispositif permettant d’injecter d’importantes quantités d’énergie renouvelable d’une part et d’autre part, en tant que composante essentielle aux grands réseaux électriques. De plus, d’énormes avantages peuvent être associés au déploiement de la technologie du BSE aussi bien dans les réseaux intelligents que pour la réduction de l’émission des gaz à effet de serre, la réduction des pertes marginales, l’alimentation de certains consommateurs en source d’énergie d’urgence, l’amélioration de la gestion de l’énergie, et l’accroissement de l’efficacité énergétique dans les réseaux. Cette présente thèse comprend trois étapes à savoir : l’Étape 1 - est relative à l’utilisation de la BSE en guise de réduction des pertes électriques ; l’Étape 2 - utilise la BSE comme élément de réserve tournante en vue de l’atténuation de la vulnérabilité du réseau ; et l’Étape 3 - introduit une nouvelle méthode d’amélioration des oscillations de fréquence par modulation de la puissance réactive, et l’utilisation de la BSE pour satisfaire la réserve primaire de fréquence. La première Étape, relative à l’utilisation de la BSE en vue de la réduction des pertes, est elle-même subdivisée en deux sous-étapes dont la première est consacrée à l’allocation optimale et le seconde, à l’utilisation optimale. Dans la première sous-étape, l’Algorithme génétique NSGA-II (Non-dominated Sorting Genetic Algorithm II) a été programmé dans CASIR, le Super-Ordinateur de l’IREQ, en tant qu’algorithme évolutionniste multiobjectifs, permettant d’extraire un ensemble de solutions pour un dimensionnement optimal et un emplacement adéquat des multiple unités de BSE, tout en minimisant les pertes de puissance, et en considérant en même temps la capacité totale des puissances des unités de BSE installées comme des fonctions objectives. La première sous-étape donne une réponse satisfaisante à l’allocation et résout aussi la question de la programmation/scheduling dans l’interconnexion du Québec. Dans le but de réaliser l’objectif de la seconde sous-étape, un certain nombre de solutions ont été retenues et développées/implantées durant un intervalle de temps d’une année, tout en tenant compte des paramètres (heure, capacité, rendement/efficacité, facteur de puissance) associés aux cycles de charge et de décharge de la BSE, alors que la réduction des pertes marginales et l’efficacité énergétique constituent les principaux objectifs. Quant à la seconde Étape, un nouvel indice de vulnérabilité a été introduit, formalisé et étudié ; indice qui est bien adapté aux réseaux modernes équipés de BES. L’algorithme génétique NSGA-II est de nouveau exécuté (ré-exécuté) alors que la minimisation de l’indice de vulnérabilité proposé et l’efficacité énergétique représentent les principaux objectifs. Les résultats obtenus prouvent que l’utilisation de la BSE peut, dans certains cas, éviter des pannes majeures du réseau. La troisième Étape expose un nouveau concept d’ajout d’une inertie virtuelle aux réseaux électriques, par le procédé de modulation de la puissance réactive. Il a ensuite été présenté l’utilisation de la BSE en guise de réserve primaire de fréquence. Un modèle générique de BSE, associé à l’interconnexion du Québec, a enfin été proposé dans un environnement MATLAB. Les résultats de simulations confirment la possibilité de l’utilisation des puissances active et réactive du système de la BSE en vue de la régulation de fréquence.

Energy Management of a Battery-Ultracapacitor Hybrid Energy Storage System in Electric Vehicles

Electric vehicle (EV) batteries tend to have accelerated degradation due to high peak power and harsh charging/discharging cycles during acceleration and deceleration periods, particularly in urban driving conditions. An oversized energy storage system (ESS) can meet the high power demands; however, it suffers from increased size, volume and cost. In order to reduce the overall ESS size and extend battery cycle life, a battery-ultracapacitor (UC) hybrid energy storage system (HESS) has been considered as an alternative solution. In this work, we investigate the optimized configuration, design, and energy management of a battery-UC HESS. One of the major challenges in a HESS is to design an energy management controller for real-time implementation that can yield good power split performance. We present the methodologies and solutions to this problem in a battery-UC HESS with a DC-DC converter interfacing with the UC and the battery. In particular, a multi-objective optimization problem is formulated to optimize the power split in order to prolong the battery lifetime and to reduce the HESS power losses. This optimization problem is numerically solved for standard drive cycle datasets using Dynamic Programming (DP). Trained using the DP optimal results, an effective real-time implementation of the optimal power split is realized based on Neural Network (NN). This proposed online energy management controller is applied to a midsize EV model with a 360V/34kWh battery pack and a 270V/203Wh UC pack. The proposed online energy management controller effectively splits the load demand with high power efficiency and also effectively reduces the battery peak current. More importantly, a 38V-385Wh battery and a 16V-2.06Wh UC HESS hardware prototype and a real-time experiment platform has been developed. The real-time experiment results have successfully validated the real-time implementation feasibility and effectiveness of the real-time controller design for the battery-UC HESS. A battery State-of-Health (SoH) estimation model is developed as a performance metric to evaluate the battery cycle life extension effect. It is estimated that the proposed online energy management controller can extend the battery cycle life by over 60%.

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.

HIGH VOLTAGE ELECTROPHORETIC DEPOSITION FOR ELECTROCHEMICAL ENERGY STORAGE AND OTHER APPLICATIONS

High voltage electrophoretic deposition (HVEPD) has been developed as a novel technique to obtain vertically aligned forests of one-dimensional nanomaterials for efficient energy storage. The ability to control and manipulate nanomaterials is critical for their effective usage in a variety of applications. Oriented structures of one-dimensional nanomaterials provide a unique opportunity to take full advantage of their excellent mechanical and electrochemical properties. However, it is still a significant challenge to obtain such oriented structures with great process flexibility, ease of processing under mild conditions and the capability to scale up, especially in context of efficient device fabrication and system packaging. This work presents HVEPD as a simple, versatile and generic technique to obtain vertically aligned forests of different one-dimensional nanomaterials on flexible, transparent and scalable substrates. Improvements on material chemistry and reduction of contact resistance have enabled the fabrication of high power supercapacitor electrodes using the HVEPD method. The investigations have also paved the way for further enhancements of performance by employing hybrid material systems and AC/DC pulsed deposition. Multi-walled carbon nanotubes (MWCNTs) were used as the starting material to demonstrate the HVEPD technique. A comprehensive study of the key parameters was conducted to better understand the working mechanism of the HVEPD process. It has been confirmed that HVEPD was enabled by three key factors: high deposition voltage for alignment, low dispersion concentration to avoid aggregation and simultaneous formation of holding layer by electrodeposition for reinforcement of nanoforests. A set of suitable parameters were found to obtain vertically aligned forests of MWCNTs. Compared with their randomly oriented counterparts, the aligned MWCNT forests showed better electrochemical performance, lower electrical resistance and a capability to achieve superhydrophpbicity, indicating their potential in a broad range of applications. The versatile and generic nature of the HVEPD process has been demonstrated by achieving deposition on flexible and transparent substrates, as well as aligned forests of manganese dioxide (MnO2) nanorods. A continuous roll-printing HVEPD approach was then developed to obtain aligned MWCNT forest with low contact resistance on large, flexible substrates. Such large-scale electrodes showed no deterioration in electrochemical performance and paved the way for practical device fabrication. The effect of a holding layer on the contact resistance between aligned MWCNT forests and the substrate was studied to improve electrochemical performance of such electrodes. It was found that a suitable precursor salt like nickel chloride could be used to achieve a conductive holding layer which helped to significantly reduce the contact resistance. This in turn enhanced the electrochemical performance of the electrodes. High-power scalable redox capacitors were then prepared using HVEPD. Very high power/energy densities and excellent cyclability have been achieved by synergistically combining hydrothermally synthesized, highly crystalline α-MnO2 nanorods, vertically aligned forests and reduced contact resistance. To further improve the performance, hybrid electrodes have been prepared in the form of vertically aligned forest of MWCNTs with branches of α-MnO2 nanorods on them. Large- scale electrodes with such hybrid structures were manufactured using continuous HVEPD and characterized, showing further improved power and energy densities. The alignment quality and density of MWCNT forests were also improved by using an AC/DC pulsed deposition technique. In this case, AC voltage was first used to align the MWCNTs, followed by immediate DC voltage to deposit the aligned MWCNTs along with the conductive holding layer. Decoupling of alignment from deposition was proven to result in better alignment quality and higher electrochemical performance.

Bidding strategy of wind-thermal energy producers

This paper presents a stochastic mixed-integer linear programming approach for solving the self-scheduling problem of a price-taker thermal and wind power producer taking part in a pool-based electricity market. Uncertainty on electricity price and wind power is considered through a set of scenarios. Thermal units are modelled by variable costs, start-up costs and technical operating constraints, such as: forbidden operating zones, ramp up/down limits and minimum up/down time limits. An efficient mixed-integer linear program is presented to develop the offering strategies of the coordinated production of thermal and wind energy generation, having as a goal the maximization of profit. A case study with data from the Iberian Electricity Market is presented and results are discussed to show the effectiveness of the proposed approach.

Revisiting compressed air energy storage.

The use of renewable energies as a response to the EU targets defined for 2030 Climate Change and Energy has been increasing. Also non-dispatchable and intermittent renewable energies like wind and solar cannot generally match supply and demand, which can also cause some problems in the grid. So, the increased interest in energy storage has evolved and there is nowadays an urgent need for larger energy storage capacity. Compressed Air Energy Storage (CAES) is a proven technology for storing large quantities of electrical energy in the form of high-pressure air for later use when electricity is needed. It exists since the 1970’s and is one of the few energy storage technologies suitable for long duration (tens of hours) and utility scale (hundreds to thousands of MW) applications. It is also one of the most cost-effective solutions for large to small scale storage applications. Compressed Air Energy Storage can be integrated and bring advantages to different levels of the electric system, from the Generation level, to the Transmission and Distribution levels, so in this paper a revisit of CAES is done in order to better understand what and how it can be used for our modern needs of energy storage.

Newly developed electrosynthesis of Layered Double Hydroxides: application to sensing, energy storage and conversion

Layered Double hydroxides (LDHs) have been widely studied for their plethora of fascinating features and applications. The potentiostatic electrodeposition of LDHs has been extensively applied in the literature as a fast and direct method to substitute classical chemical routes. However, it does not usually allow for a fine control of the M(II)/M(III) ratio in the synthesized material and it is not suitable for large anions intercalation. Therefore, in this work a novel protocol has been proposed with the aim to overcome all these constraints using a method based on potentiodynamic synthesis. LDHs of controlled composition were prepared using different molar ratios of the trivalent to bivalent cations in the electrolytic solution ranging from 1:1 to 1:4. Moreover, we were able to produce electrochemically LDHs intercalated with carbon nanomaterials for the first time. A one-step procedure which contemporaneously allows for the Ni/Al-LDH synthesis, the reduction of graphene oxide (GO) and its intercalation inside the structure has been developed. The synthesised materials have been applied in several fields of interest. First of all, LDHs with a ratio 3:1 were exploited, and displayed good performances as catalysts for 5-(hydroxymethyl)furfural electro-oxidation, thus suggesting to carry out further investigation for applications in the field of industrial catalysis. The same materials, but with different metals ratios, were tested as catalysts for Oxygen Evolution Reaction, obtaining results comparable to LDHs synthesised by the classical co-precipitation method and also a better activity with respect to LDHs obtained by the potentiostatic approach. The composite material based on LDH and reduced graphene oxide was employed to fabricate a cathode of a hybrid supercapacitor coupled with an activated carbon anode. We can thus conclude that, to date, the potentiodynamic method has the greatest potential for the rapid synthesis of reproducible films of Co and Ni-based LDHs with controlled composition.

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.

Analysis of the impact of stationary energy storage systems in trolleybus grids using Simulink-based modelling

The voltage profile of the catenary between traction substations (TSSs) is affected by the trolleybus current intake and by its position with respect to the TSSs: the higher the current requested by the bus and the further the bus from the TSSs, the deeper the voltage drop. When the voltage drops below 500V, the trolleybus is forced to decrease its consumption by reducing its input current. This thesis deals with the analysis of the improvements that the installation of an BESS produces in the operation of a particularly loaded FS of the DC trolleybus network of the city of Bologna. The stationary BESS is charged by the TSSs during off-peak times and delivers the stored energy when the catenary is overloaded alleviating the load on the TSSs and reducing the voltage drops. Only IMC buses are considered in the prospect of a future disposal of all internal combustion engine vehicles. These trolleybuses cause deeper voltage drops because they absorb enough current to power their traction motor and recharge the on board battery. The control of the BESS aims to keep the catenary voltage within the admissible voltage range and makes sure that all physical limitations are met. A model of FS Marconi Trento Trieste is implemented in Simulink environment to simulate its daily operation and compare the behavior of the trolleybus network with and without BESS. From the simulation without BESS, the best location of the energy storage system is deduced, and the battery control is tuned. Furthermore, from the knowledge of the load curve and the battery control trans-characteristic, it is formulated a prediction of the voltage distribution at BESS connection point. The prediction is then compared with the simulation results to validate the Simulink model. The BESS allows to decrease the voltage drops along the catenary, the Joule losses and the current delivered by the TSSs, indicating that the BESS can be a solution to improve the operation of the trolleybus network.

Design and Off-design modelling of advanced Power-to-Gas energy storage systems

Power-to-Gas storage systems have the potential to address grid-stability issues that arise when an increasing share of power is generated from sources that have a highly variable output. Although the proof-of-concept of these has been promising, the behaviour of the processes in off-design conditions is not easily predictable. The primary aim of this PhD project was to evaluate the performance of an original Power-to-Gas system, made up of innovative components. To achieve this, a numerical model has been developed to simulate the characteristics and the behaviour of the several components when the whole system is coupled with a renewable source. The developed model has been applied to a large variety of scenarios, evaluating the performance of the considered process and exploiting a limited amount of experimental data. The model has been then used to compare different Power-to-Gas concepts, in a real scenario of functioning. Several goals have been achieved. In the concept phase, the possibility to thermally integrate the high temperature components has been demonstrated. Then, the parameters that affect the energy performance of a Power-to-Gas system coupled with a renewable source have been identified, providing general recommendations on the design of hybrid systems; these parameters are: 1) the ratio between the storage system size and the renewable generator size; 2) the type of coupled renewable source; 3) the related production profile. Finally, from the results of the comparative analysis, it is highlighted that configurations with a highly oversized renewable source with respect to the storage system show the maximum achievable profit.

Polyaniline-based materials and nanocomposites: from energy storage to sensing applications

The research work described in this thesis concerns materials for both energy storage and sensoristics applications. Firstly, the synthesis and characterization of magnetite (Fe3O4) functionalyzed with [3-(2-propynylcarbamate)propyl]triethoxysilane (PPTEOS) capable to reduce the gold precursor chloroauric acid (HAuCl4) without the need of additional reducing or stabilising agents is described. These nanoparticles were tested to improve performances of symmetric capacitors based on polyaniline and graphite foil. Energy storage applications were investigated also during six months stay at EPFL University of Lausanne where an investigation about different tailored catalysts for Oxygen Evolution Reaction in a particular Redox Flow Battery was carried out. For what concerns sensing applications, new materials based on cellulose modified with polyaniline and poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAAMPSA) were synthesized, characterized and applied to monitor pressure, humidity, heart rate and lastly, bread fermentation in collaboration with the University of Fribourg and Zurich. The characterizations of all the materials investigated compriseed numerous techniques such as infrared attenuated total reflectance spectroscopy (IR-ATR), thermogravimetric analysis (TGA), scanning and transmission electron microscopy (SEM and TEM), alongside linear and cyclic voltammetry (LSV and CV), electrochemical impedance spectroscopy (EIS) and chronoamperometric analyses.

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.

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.