Nanocrystalline Silicon Based Films for Renewable Energy Applications

The present thesis is focused on the study of innovative Si-based materials for third generation photovoltaics. In particular, silicon oxi-nitride (SiOxNy) thin films and multilayer of Silicon Rich Carbide (SRC)/Si have been characterized in view of their application in photovoltaics. SiOxNy is a promising material for applications in thin-film solar cells as well as for wafer based silicon solar cells, like silicon heterojunction solar cells. However, many issues relevant to the material properties have not been studied yet, such as the role of the deposition condition and precursor gas concentrations on the optical and electronic properties of the films, the composition and structure of the nanocrystals. The results presented in the thesis aim to clarify the effects of annealing and oxygen incorporation within nc-SiOxNy films on its properties in view of the photovoltaic applications. Silicon nano-crystals (Si NCs) embedded in a dielectric matrix were proposed as absorbers in all-Si multi-junction solar cells due to the quantum confinement capability of Si NCs, that allows a better match to the solar spectrum thanks to the size induced tunability of the band gap. Despite the efficient solar radiation absorption capability of this structure, its charge collection and transport properties has still to be fully demonstrated. The results presented in the thesis aim to the understanding of the transport mechanisms at macroscopic and microscopic scale. Experimental results on SiOxNy thin films and SRC/Si multilayers have been obtained at macroscopical and microscopical level using different characterizations techniques, such as Atomic Force Microscopy, Reflection and Transmission measurements, High Resolution Transmission Electron Microscopy, Energy-Dispersive X-ray spectroscopy and Fourier Transform Infrared Spectroscopy. The deep knowledge and improved understanding of the basic physical properties of these quite complex, multi-phase and multi-component systems, made by nanocrystals and amorphous phases, will contribute to improve the efficiency of Si based solar cells.

Experimental and Numerical Analysis of Gas Forced Convection through Microtubes and Micro Heat Exchangers

The last decade has witnessed very fast development in microfabrication technologies. The increasing industrial applications of microfluidic systems call for more intensive and systematic knowledge on this newly emerging field. Especially for gaseous flow and heat transfer at microscale, the applicability of conventional theories developed at macro scale is not yet completely validated; this is mainly due to scarce experimental data available in literature for gas flows. The objective of this thesis is to investigate these unclear elements by analyzing forced convection for gaseous flows through microtubes and micro heat exchangers. Experimental tests have been performed with microtubes having various inner diameters, namely 750 m, 510 m and 170 m, over a wide range of Reynolds number covering the laminar region, the transitional zone and also the onset region of the turbulent regime. The results show that conventional theory is able to predict the flow friction factor when flow compressibility does not appear and the effect of fluid temperature-dependent properties is insignificant. A double-layered microchannel heat exchanger has been designed in order to study experimentally the efficiency of a gas-to-gas micro heat exchanger. This microdevice contains 133 parallel microchannels machined into polished PEEK plates for both the hot side and the cold side. The microchannels are 200 µm high, 200 µm wide and 39.8 mm long. The design of the micro device has been made in order to be able to test different materials as partition foil with flexible thickness. Experimental tests have been carried out for five different partition foils, with various mass flow rates and flow configurations. The experimental results indicate that the thermal performance of the countercurrent and cross flow micro heat exchanger can be strongly influenced by axial conduction in the partition foil separating the hot gas flow and cold gas flow.

Development of a microgrid with renewable energy sources and electrochemical storage system integration

Beside the traditional paradigm of "centralized" power generation, a new concept of "distributed" generation is emerging, in which the same user becomes pro-sumer. During this transition, the Energy Storage Systems (ESS) can provide multiple services and features, which are necessary for a higher quality of the electrical system and for the optimization of non-programmable Renewable Energy Source (RES) power plants. A ESS prototype was designed, developed and integrated into a renewable energy production system in order to create a smart microgrid and consequently manage in an efficient and intelligent way the energy flow as a function of the power demand. The produced energy can be introduced into the grid, supplied to the load directly or stored in batteries. The microgrid is composed by a 7 kW wind turbine (WT) and a 17 kW photovoltaic (PV) plant are part of. The load is given by electrical utilities of a cheese factory. The ESS is composed by the following two subsystems, a Battery Energy Storage System (BESS) and a Power Control System (PCS). With the aim of sizing the ESS, a Remote Grid Analyzer (RGA) was designed, realized and connected to the wind turbine, photovoltaic plant and the switchboard. Afterwards, different electrochemical storage technologies were studied, and taking into account the load requirements present in the cheese factory, the most suitable solution was identified in the high temperatures salt Na-NiCl2 battery technology. The data acquisition from all electrical utilities provided a detailed load analysis, indicating the optimal storage size equal to a 30 kW battery system. Moreover a container was designed and realized to locate the BESS and PCS, meeting all the requirements and safety conditions. Furthermore, a smart control system was implemented in order to handle the different applications of the ESS, such as peak shaving or load levelling.

Development of methodologies supporting the sustainable and safe integration of offshore conventional and renewable energy production

Against a backdrop of rapidly increasing worldwide population and growing energy demand, the development of renewable energy technologies has become of primary importance in the effort to reduce greenhouse gas emissions. However, it is often technically and economically infeasible to transport discontinuous renewable electricity for long distances to the shore. Another shortcoming of non-programmable renewable power is its integration into the onshore grid without affecting the dispatching process. On the other hand, the offshore oil & gas industry is striving to reduce overall carbon footprint from onsite power generators and limiting large expenses associated to carrying electricity from remote offshore facilities. Furthermore, the increased complexity and expansion towards challenging areas of offshore hydrocarbons operations call for higher attention to safety and environmental protection issues from major accident hazards. Innovative hybrid energy systems, as Power-to-Gas (P2G), Power-to-Liquid (P2L) and Gas-to-Power (G2P) options, implemented at offshore locations, would offer the opportunity to overcome challenges of both renewable and oil & gas sectors. This study aims at the development of systematic methodologies based on proper sustainability and safety performance indicators supporting the choice of P2G, P2L and G2P hybrid energy options for offshore green projects in early design phases. An in-depth analysis of the different offshore hybrid strategies was performed. The literature reviews on existing methods proposing metrics to assess sustainability of hybrid energy systems, inherent safety of process routes in conceptual design stage and environmental protection of installations from oil and chemical accidental spills were carried out. To fill the gaps, a suite of specific decision-making methodologies was developed, based on representative multi-criteria indicators addressing technical, economic, environmental and societal aspects of alternative options. A set of five case-studies was defined, covering different offshore scenarios of concern, to provide an assessment of the effectiveness and value of the developed tools.

Sustainable exploitation of offshore renewable energy sources

Energy transition is the response of humankind to the concerning effects of fossil fuels depletion, climate change and energy insecurity, and calls for a deep penetration of renewable energy sources (RESs) in power systems and industrial processes. Despite the high potentials, low impacts and long-term availability, RESs present some limits which need to be overcome, such as the strong variability and difficult predictability, which result in scarce reliability and difficult applicability in steady-state processes. Some technological solutions relate to energy storage systems, equipment electrification and hybrid systems deployment, thus accomplishing distributed generation even in remote sites as offshore. However, all of these actions cannot disregard sustainability, which represents a founding principle for any project, bringing together economics, reliability and environmental protection. To entail sustainability in RESs-based innovative projects, previous knowledge and tools are often not tailored or miss the novel objectives. This research proposes three methodological approaches, bridging the gaps. The first contribute adapts literature-based indicators of inherent safety and energy efficiency to capture the specificities of novel process plants and hybrid systems. Minor case studies dealing with novel P2X processes exemplify the application of these novel indicators. The second method guides the conceptual design of hybrid systems for the valorisation of a RES in a site, by considering the sustainability performances of alternative design options. Its application is demonstrated through the comparison of two offshore sites where wave energy can be valorised. Finally, “OHRES”, a comprehensive tool for the sustainable optimisation of hybrid renewable energy systems is proposed. “OHRES” hinges on the exploitation of multiple RESs, by converting ex-post sustainability indicators into discrimination markers screening a large number of possible system configurations, according to the location features. Five case studies demonstrate “OHRES” versatility in the sustainable valorisation of multiple RESs.

Realizzazione di riporti funzionalizzanti su superfici ceramiche per la produzione di energia elettrica mediante effetto fotovoltaico

This research, carried out during the PhD in Materials Engineering, deals with the creation of layers, with different functionality, deposited on a ceramic substrate, to obtain photovoltaic cells for electricity production. The research activities are included in the project PRRIITT, Measure 4 (Development of Networks), Action A (Research and Technology Transfer Laboratories), Thematic reference 3 (Advanced materials applications development), co-financed by the Emilia Romagna Region, for the creation of CECERBENCH laboratory, which aims to develop "Tiles with a functionalised surface”. The innovation lies in the study of materials and in the development of technologies to achieve a "photovoltaic surface", directly in the tiles production process. The goal is to preserve the technical characteristics, and to make available new surfaces, exploiting renewable energy sources. The realization of Building Integrated PhotoVoltaic (BIPV) is nowadays a more and more spread tendency. The aims of the research are essentially linked to the need to diversify the actual ceramic tile production (which is strongly present in the Emilia Romagna Region ), and to provide a higher added value to the tiles. Solar energy production is the primary objective of the functionalization, and has a relevant ecological impact, taking into account the overwhelming global energy demand. The specific activities of the PhD were carried out according to the achievement of scientific and technological objectives of CECERBENCH laboratory, and involved the collaboration in design solutions, to obtain the cells directly on the tiles surface. The author has managed personally a part of the research project. Layers with different features were made: - Electrically conductive layers, directly on the ceramic tiles surface; - Layers to obtain the photovoltaic functionality; - Electrically insulating, protective layers (double function). For each layer, the most suitable materials have been selected. Among the technical application, the screen printing was used. This technique, widely used in ceramics, has many application areas, including the electronics and photovoltaic industries. It is an inexpensive technique, easy to use in industrial production lines. The screen printing technique was therefore studied in depth by theoretical considerations, and through the use of rheological measurements.

Theoretical and Experimental Analysis of micro-CHP Energy Systems

In the framework of the micro-CHP (Combined Heat and Power) energy systems and the Distributed Generation (GD) concept, an Integrated Energy System (IES) able to meet the energy and thermal requirements of specific users, using different types of fuel to feed several micro-CHP energy sources, with the integration of electric generators of renewable energy sources (RES), electrical and thermal storage systems and the control system was conceived and built. A 5 kWel Polymer Electrolyte Membrane Fuel Cell (PEMFC) has been studied. Using experimental data obtained from various measurement campaign, the electrical and CHP PEMFC system performance have been determinate. The analysis of the effect of the water management of the anodic exhaust at variable FC loads has been carried out, and the purge process programming logic was optimized, leading also to the determination of the optimal flooding times by varying the AC FC power delivered by the cell. Furthermore, the degradation mechanisms of the PEMFC system, in particular due to the flooding of the anodic side, have been assessed using an algorithm that considers the FC like a black box, and it is able to determine the amount of not-reacted H2 and, therefore, the causes which produce that. Using experimental data that cover a two-year time span, the ageing suffered by the FC system has been tested and analyzed.

Aspetti di sostenibilità in agricoltura a diverse scale spaziali e temporali. Valutazioni ambientali, economiche ed energetiche.

La Tesi analizza le relazioni tra i processi di sviluppo agricolo e l’uso delle risorse naturali, in particolare di quelle energetiche, a livello internazionale (paesi in via di sviluppo e sviluppati), nazionale (Italia), regionale (Emilia Romagna) e aziendale, con lo scopo di valutare l’eco-efficienza dei processi di sviluppo agricolo, la sua evoluzione nel tempo e le principali dinamiche in relazione anche ai problemi di dipendenza dalle risorse fossili, della sicurezza alimentare, della sostituzione tra superfici agricole dedicate all’alimentazione umana ed animale. Per i due casi studio a livello macroeconomico è stata adottata la metodologia denominata “SUMMA” SUstainability Multi-method, multi-scale Assessment (Ulgiati et al., 2006), che integra una serie di categorie d’impatto dell’analisi del ciclo di vita, LCA, valutazioni costi-benefici e la prospettiva di analisi globale della contabilità emergetica. L’analisi su larga scala è stata ulteriormente arricchita da un caso studio sulla scala locale, di una fattoria produttrice di latte e di energia elettrica rinnovabile (fotovoltaico e biogas). Lo studio condotto mediante LCA e valutazione contingente ha valutato gli effetti ambientali, economici e sociali di scenari di riduzione della dipendenza dalle fonti fossili. I casi studio a livello macroeconomico dimostrano che, nonostante le politiche di supporto all’aumento di efficienza e a forme di produzione “verdi”, l’agricoltura a livello globale continua ad evolvere con un aumento della sua dipendenza dalle fonti energetiche fossili. I primi effetti delle politiche agricole comunitarie verso una maggiore sostenibilità sembrano tuttavia intravedersi per i Paesi Europei. Nel complesso la energy footprint si mantiene alta poiché la meccanizzazione continua dei processi agricoli deve necessariamente attingere da fonti energetiche sostitutive al lavoro umano. Le terre agricole diminuiscono nei paesi europei analizzati e in Italia aumentando i rischi d’insicurezza alimentare giacché la popolazione nazionale sta invece aumentando.

Soil organic carbon dynamics under perennial energy crops

The European renewable energy directive 2009/28/EC (E.C. 2009) provides a legislative framework for reducing GHG emissions by 20%, while achieving a 20% share of energy from renewable sources by 2020. Perennial energy crops could significantly contribute to limit GHG emissions through replacing equivalent fossil fuels and by sequestering a considerable amount of carbon into the soil through the large amounts of belowground biomass produced. The objective of this study is to evaluate the effects of land use change that perennial energy crops have on croplands (switchgrass) and marginal grasslands (miscanthus). For that purpose above and belowground biomass, SOC variation and Net Ecosystem Exchange were evaluated after five years of growth. At aboveground level both crops produced high biomass under cropland conditions as well as under marginal soils. At belowground level they also produced large amounts of biomass, but no significant influences on SOC in the upper layer (0-30 cm) were found. This is probably because of the "priming effect" that caused fast carbon substitution. In switchgrass only it was found a significant SOC increase in deeper layers (30-60 cm), while in the whole soil profile (0-60 cm) SOC increased from 42 to 51 ha-1. However, the short experimental periods (for both switchgrass and miscanthus), in which land use change was evaluated, do not permit to determine the real capacity of perennial energy crops to accumulate SOC. In conclusion the large amounts of belowground biomass enhanced the SOC dynamic through the priming effect resulting in increased SOC in cropland but not in marginal grassland.

Design and experimental characterization of antennas and wireless systems for innovative wearable and implantable ultra low–power applications

The present PhD thesis exploits the design skills I have been improving since my master thesis’ research. A brief description of the chapters’ content follows. Chapter 1: the simulation of a complete front–end is a very complex problem and, in particular, is the basis upon which the prediction of the overall performance of the system is possible. By means of a commercial EM simulation tool and a rigorous nonlinear/EM circuit co–simulation based on the Reciprocity Theorem, the above–mentioned prediction can be achieved and exploited for wireless links characterization. This will represent the theoretical basics of the entire present thesis and will be supported by two RF applications. Chapter 2: an extensive dissertation about Magneto–Dielectric (MD) materials will be presented, together with their peculiar characteristics as substrates for antenna miniaturization purposes. A designed and tested device for RF on–body applications will be described in detail. Finally, future research will be discussed. Chapter 3: this chapter will deal with the issue regarding the exploitation of renewable energy sources for low–energy consumption devices. Hence the problem related to the so–called energy harvesting will be tackled and a first attempt to deploy THz solar energy in an innovative way will be presented and discussed. Future research will be proposed as well. Chapter 4: graphene is a very promising material for devices to be exploited in the RF and THz frequency range for a wide range of engineering applications, including those ones marked as the main research goal of the present thesis. This chapter will present the results obtained during my research period at the National Institute for Research and Development in Microtechnologies (IMT) in Bucharest, Romania. It will concern the design and manufacturing of antennas and diodes made in graphene–based technology for detection/rectification purposes.

Teoria e pratica dell'architettura solare - Morfologia, rendimento, strategia progettuale

La recente Direttiva 31/2010 dell’Unione Europea impone agli stati membri di riorganizzare il quadro legislativo nazionale in materia di prestazione energetica degli edifici, affinchè tutte le nuove costruzioni presentino dal 1° gennaio 2021 un bilancio energetico tendente allo zero; termine peraltro anticipato al 1° gennaio 2019 per gli edifici pubblici. La concezione di edifici a energia “quasi” zero (nZEB) parte dal presupposto di un involucro energeticamente di standard passivo per arrivare a compensare, attraverso la produzione preferibilmente in sito di energia da fonti rinnovabili, gli esigui consumi richiesti su base annuale. In quest’ottica la riconsiderazione delle potenzialità dell’architettura solare individua degli strumenti concreti e delle valide metodologie per supportare la progettazione di involucri sempre più performanti che sfruttino pienamente una risorsa inesauribile, diffusa e alla portata di tutti come quella solare. Tutto ciò in considerazione anche della non più procrastinabile necessità di ridurre il carico energetico imputabile agli edifici, responsabili come noto di oltre il 40% dei consumi mondiali e del 24% delle emissioni di gas climalteranti. Secondo queste premesse la ricerca pone come centrale il tema dell’integrazione dei sistemi di guadagno termico, cosiddetti passivi, e di produzione energetica, cosiddetti attivi, da fonte solare nell’involucro architettonico. Il percorso sia analitico che operativo effettuato si è posto la finalità di fornire degli strumenti metodologici e pratici al progetto dell’architettura, bisognoso di un nuovo approccio integrato mirato al raggiungimento degli obiettivi di risparmio energetico. Attraverso una ricognizione generale del concetto di architettura solare e dei presupposti teorici e terminologici che stanno alla base della stessa, la ricerca ha prefigurato tre tipologie di esito finale: una codificazione delle morfologie ricorrenti nelle realizzazioni solari, un’analisi comparata del rendimento solare nelle principali aggregazioni tipologiche edilizie e una parte importante di verifica progettuale dove sono stati applicati gli assunti delle categorie precedenti

From fossil to sustainable diets: an assessment of farming energy footprint

The dependence of industrial agricolture on fossil fuels has been assessed in two comparative case studies between Italy (Emilia-Romagna and Piemonte)and Missouri. The first is related to dairy farming; 15 different farms were surveyed, divided into three different groups: grain based, pasture based and organic. The second is devoted to rice cropping; 12 holdings were examined divided into two groups: conventional and organic. Energy footprint was determined for structures, machinery, fertilizers, pesticides, fuel, electricity, feed and seeds. Possible scenarios of transition to a more sustainable agricolture based on renewable energy sources were analized in detail for all the farms analized.

Distributed Large-scale Mixed-Integer Optimization with Application to Energy and Multi-robot Networks

Several decision and control tasks in cyber-physical networks can be formulated as large- scale optimization problems with coupling constraints. In these "constraint-coupled" problems, each agent is associated to a local decision variable, subject to individual constraints. This thesis explores the use of primal decomposition techniques to develop tailored distributed algorithms for this challenging set-up over graphs. We first develop a distributed scheme for convex problems over random time-varying graphs with non-uniform edge probabilities. The approach is then extended to unknown cost functions estimated online. Subsequently, we consider Mixed-Integer Linear Programs (MILPs), which are of great interest in smart grid control and cooperative robotics. We propose a distributed methodological framework to compute a feasible solution to the original MILP, with guaranteed suboptimality bounds, and extend it to general nonconvex problems. Monte Carlo simulations highlight that the approach represents a substantial breakthrough with respect to the state of the art, thus representing a valuable solution for new toolboxes addressing large-scale MILPs. We then propose a distributed Benders decomposition algorithm for asynchronous unreliable networks. The framework has been then used as starting point to develop distributed methodologies for a microgrid optimal control scenario. We develop an ad-hoc distributed strategy for a stochastic set-up with renewable energy sources, and show a case study with samples generated using Generative Adversarial Networks (GANs). We then introduce a software toolbox named ChoiRbot, based on the novel Robot Operating System 2, and show how it facilitates simulations and experiments in distributed multi-robot scenarios. Finally, we consider a Pickup-and-Delivery Vehicle Routing Problem for which we design a distributed method inspired to the approach of general MILPs, and show the efficacy through simulations and experiments in ChoiRbot with ground and aerial robots.

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.

Development of processes for the valorization of lignocellulosic biomass based on renewable energies

The world grapples with climate change from fossil fuel reliance, prompting Europe to pivot to renewable energy. Among renewables, biomass is a bioenergy and bio-carbon source, used to create high-value biomolecules, replacing fossil-based products. Alkyl levulinates, derived from biomass, hold promise as bio-additives and biofuels, especially via acid solvolysis of hexose sugars, necessitating further exploration. Alkyl levulinate's potential extends to converting into γ-valerolactone (GVL), a bio-solvent produced via hydrogenation with molecular-hydrogen. Hydrogen, a key reagent and energy carrier, aids renewable energy integration. This thesis delves into a biorefinery system study, aligning with sustainability goals, integrating biomass valorization, energy production, and hydrogen generation. It investigates optimizing technologies for butyl levulinate production and subsequent GVL hydrogenation. Sustainability remains pivotal, reflecting the global shift towards renewable and carbon bio-resources. The research initially focuses on experimenting with the optimal technology for producing butyl levulinate from biomass-derived hexose fructose. It examines the solvolysis process, investigating optimal conditions, kinetic modeling, and the impact of solvents on fructose conversion. The subsequent part concentrates on the technological aspect of hydrogenating butyl levulinate into GVL. It includes conceptual design, simulation, and optimization of the fructose-to-GVL process scheme based on process intensification. In the final part, the study applies the process to a real case study in Normandy, France, adapting it to local biomass availability and wind energy. It defines a methodology for designing and integrating the energy-supply system, evaluating different scenarios. Sustainability assessment using economic, environmental, and social indicators culminates in an overall sustainability index, indicating scenarios integrating the GVL biorefinery system with wind power and hydrogen energy storage as promising due to high profitability and reduced environmental impact. Sensitivity analyses validate the methodology's reliability, potentially extending to other technological systems.