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.

Development of an innovative non rule-based energy management strategy for a Hybrid Electric Vehicle, structured for predictive driving controls based on external information knowledge

Recently, the interest of the automotive market for hybrid vehicles has increased due to the more restrictive pollutants emissions legislation and to the necessity of decreasing the fossil fuel consumption, since such solution allows a consistent improvement of the vehicle global efficiency. The term hybridization regards the energy flow in the powertrain of a vehicle: a standard vehicle has, usually, only one energy source and one energy tank; instead, a hybrid vehicle has at least two energy sources. In most cases, the prime mover is an internal combustion engine (ICE) while the auxiliary energy source can be mechanical, electrical, pneumatic or hydraulic. It is expected from the control unit of a hybrid vehicle the use of the ICE in high efficiency working zones and to shut it down when it is more convenient, while using the EMG at partial loads and as a fast torque response during transients. However, the battery state of charge may represent a limitation for such a strategy. That’s the reason why, in most cases, energy management strategies are based on the State Of Charge, or SOC, control. Several studies have been conducted on this topic and many different approaches have been illustrated. The purpose of this dissertation is to develop an online (usable on-board) control strategy in which the operating modes are defined using an instantaneous optimization method that minimizes the equivalent fuel consumption of a hybrid electric vehicle. The equivalent fuel consumption is calculated by taking into account the total energy used by the hybrid powertrain during the propulsion phases. The first section presents the hybrid vehicles characteristics. The second chapter describes the global model, with a particular focus on the energy management strategies usable for the supervisory control of such a powertrain. The third chapter shows the performance of the implemented controller on a NEDC cycle compared with the one obtained with the original control strategy.

Surfing the high energy output branch of nonlinear energy harvesters

Hysteresis and multistability are fundamental phenomena of driven nonlinear oscillators, which, however, restrict many applications such as mechanical energy harvesting. We introduce an electrical control mechanism to switch from the low to the high energy output branch of a nonlinear energy harvester by exploiting the strong interplay between its electrical and mechanical degrees of freedom. This method improves the energy conversion efficiency over a wide bandwidth in a frequency-amplitude-varying environment using only a small energy budget. The underlying effect is independent of the device scale and the transduction method and is explained using a modified Duffing oscillator model.

A Generalized hierarchical transactive energy management framework for residential microgrids

This work develops a transactive energy management system in order to automate the operation and efficiently utilize the energy generated from the solar PV unit and BESS in a single house as well as in the microgrid and provides cost-benefit analysis.

Multi-agent approach for enhancing security of protection schemes in cyber-physical energy systems

This paper presents a distributed multi-agent scheme to detect and identify cyber threats on the protection systems of power grids. The integration of information and communication technologies (ICTs) into existing power grids builds critical cyberphysical energy systems CPESs) in which digital relays are networked cyber-physical components subject to various cyber threats. Cyber attacks on protection systems may mimic real faults, cause component failure, and disable the communication links. Agents utilize both cyber and physical properties to reinforce the detection technique and further distinguish cyber attacks from physical faults. This paper also introduces the problem of secure communicationprotocols and highlights the comparative studies for enhancing thesecurity of the protection systems. The proposed scheme is validatedusing a benchmark power system under various fault and cyber attack scenarios.

Energy consumption and energy efficiency in olive oil mills: case studies in Portugal and Spain in the frame of TESLA project

TESLA project (Transfering Energy Save Laid on Agroindustry) financed by the European Commission, had the main goals of evaluating the energy consumption and to identify the best available practices to improve energy efficiency in key agro-food sectors, such as the olive oil mills. A general analysis of energy consumptions allowed identifying the partition between electrical and thermal energy (approximately 50%) and the production processes responsible for the higher energy consumptions, as being the in the mill and paste preparation and the phases separation. Some measures for reducing energy waste and for improving energy efficiency were identified and the impact was evaluated by using the TESLA tool developed by Circe and available at the TESLA website.

Load Profile Analysis Tool for Electrical Appliances in Households

This paper presents a methodology to forecast the hourly and daily consumption in households. The methodology was validated for households in Lisbon region, Portugal. The paper shows that the forecast tool allows obtaining satisfactory results for forecasting. Models of demand response allow the support of consumer’s decision in exchange for an economic benefit by the redefinition of load profile or changing the appliance consumption period. It is also in the interest of electric utilities to take advantage of these changes, particularly when consumers have an action on the demand-side management or production. Producers need to understand the load profile of households that are connected to a smart grid, to promote a better use of energy, as well as optimize the use of micro-generation from renewable sources, not only to delivering to the network but also in self-consumption.

Load Profile Analysis Tool for Electrical Appliances in Households Assisted by CPS

This paper presents a methodology to forecast the hourly and daily consumption in households assisted by cyber physical systems. The methodology was validated using a database of consumption of a set of 93 domestic consumers. Forecast tools used were based on Fast Fourier Series and Generalized Reduced Gradient. Both tools were tested and their forecast results were compared. The paper shows that both tools allow obtaining satisfactory results for energy consumption forecasting.

Advances in integration of photovoltaic power and energy production in practical systems

This thesis presents advances in integration of photovoltaic (PV) power and energy in practical systems, such as existing power plants in buildings or directly integrated in the public electrical grid. It starts by providing an analyze of the current state of PV power and some of its limitations. The work done in this thesis begins by providing a model to compute mutual shading in large PV plants, and after provides a study of the integration of a PV plant in a biogas power plant. The remainder sections focus on the work done for project PVCROPS, which consisted on the construction and operation of two prototypes composed of a PV system and a novel battery connected to a building and to the public electrical grid. These prototypes were then used to test energy management strategies and validate the suitability of the two advanced batteries (a lithium-ion battery and a vanadium redox ow battery) for households (BIPV) and PV plants. This thesis is divided in 7 chapters: Chapter 1 provides an introduction to explain and develop the main research questions studied for this thesis; Chapter 2 presents the development of a ray-tracing model to compute shading in large PV elds (with or without trackers); Chapter 3 shows the simulation of hybridizing a biogas plant with a PV plant, using biogas as energy storage; Chapters 4 and 5 present the construction, programming, and initial operation of both prototypes (Chapter 4), EMS testing oriented to BIPV systems (Chapter 5). Finally, Chapters 6 provides some future lines of investigation that can follow this thesis, and Chapter 7 shows a synopsis of the main conclusions of this work; Resumo: Avanços na integracão de potência fotovoltaica e producão de energia em sistemas práticos Esta tese apresenta avanços na integração de potência e energia fotovoltaica (PV) em sistemas práticos, tais como centrais existentes ou a rede eléctrica pública. Come ça por analisar o estado corrente do fotovoltaico no mundo e aborda algumas das suas limitações. O trabalho feito para esta tese de doutoramento começou pelo desenvolvimento de um modelo para calcular os sombreamentos que ocorrem em grandes campos fotovoltaicos, e depois apresenta um estudo sobre a integração um sistema fotovoltaico em uma central eléctrica a bióg as. As ultimas secções da tese focam-se no trabalho feito para o projecto PVCROPS, que consistiu na construção e operação de dois demonstratores, cada um formado por um sistema fotovoltaico e bateria conectados a um edíficio e a rede eléctrica pública. Estes protótipos foram posteriormente utilizados para testar estratégias de gestão de energia (EMS) e para validar a operação de duas baterias avançadas (bateria de Iões de Li tio e bateria de Fluxo Redox de Van adio) e a sua utiliza ção para habitações e centrais PV. A tese está dividida em 7 capitulos: O capitulo 1 apresenta uma introdução para explicar e desenvolver as principais questões que foram investigadas nesta tese; O capitulo 2 mostra o desenvolvimento de um modelo baseado em traçados de raios para calcular sombreamentos mútuos em grandes centrais PV (com e sem seguidores); O capitulo 3 mostra a simulação da hibridização de uma central electrica a biogas com uma central PV, e utilizando o biógas como armazenamento de energia. Os capitulos 4 e 5 apresentam a construção, programação e operação inicial dos dois demonstradores (Capitúlo 4), o teste de EMS orientadas para sistemas PV em habitações (Capítulo 5). Finalmente, o capítulo 6 sugere algumas futuras linhas de investigação que poderão seguir esta tese, e o Capítulo 7 faz uma sinopse das principais conclusões deste trabalho.

Clinical Accuracy of the MedGem Indirect Calorimeter for Measuring Resting Energy Expenditure in Cancer Patients

OBJECTIVE: To compare, in patients with cancer and in healthy subjects, measured resting energy expenditure (REE) from traditional indirect calorimetry to a new portable device (MedGem) and predicted REE. DESIGN: Cross-sectional clinical validation study. SETTING: Private radiation oncology centre, Brisbane, Australia. SUBJECTS: Cancer patients (n = 18) and healthy subjects (n = 17) aged 37-86 y, with body mass indices ranging from 18 to 42 kg/m(2). INTERVENTIONS: Oxygen consumption (VO(2)) and REE were measured by VMax229 (VM) and MedGem (MG) indirect calorimeters in random order after a 12-h fast and 30-min rest. REE was also calculated from the MG without adjustment for nitrogen excretion (MGN) and estimated from Harris-Benedict prediction equations. Data were analysed using the Bland and Altman approach, based on a clinically acceptable difference between methods of 5%. RESULTS: The mean bias (MGN-VM) was 10% and limits of agreement were -42 to 21% for cancer patients; mean bias -5% with limits of -45 to 35% for healthy subjects. Less than half of the cancer patients (n = 7, 46.7%) and only a third (n = 5, 33.3%) of healthy subjects had measured REE by MGN within clinically acceptable limits of VM. Predicted REE showed a mean bias (HB-VM) of -5% for cancer patients and 4% for healthy subjects, with limits of agreement of -30 to 20% and -27 to 34%, respectively. CONCLUSIONS: Limits of agreement for the MG and Harris Benedict equations compared to traditional indirect calorimetry were similar but wide, indicating poor clinical accuracy for determining the REE of individual cancer patients and healthy subjects.

Efficient microwave hydrothermal preparation of nanocrystalline anatase TiO2 colloids

Titanium dioxide nanocrystals are an important commercial product used primarily in white pigments and abrasives, however, more recently the anatase form of TiO2 has become a major component in electrochemical and photoelectrochemical devices. An important property of titanium dioxide nanocrystals for electrical applications is the degree of crystallinity. Numerous preparation methods exist for the production of highly crystalline TiO2 particles. The majority of these processes require long reaction times, high pressures and temperatures (450–1400 °C). Recently, hydrothermal treatment of colloidal TiO2 suspensions has been shown to produce quality crystalline products at low temperatures (<250 °C). In this paper we extend this idea utilising a direct microwave heating source. A comparison between convection and microwave hydrothermal treatment of colloidal TiO2 is presented. The resulting highly crystalline TiO2 colloids were characterised using Raman spectroscopy, XRD, TEM, and electron diffraction. The results show that the microwave treatment of colloidal TiO2 gives comparable increases in crystallinity with respect to normal hydrothermal treatments while requiring significantly less time and energy than the hydrothermal convection treatment.