Electrode Materials for Ionic Liquid Based-Supercapacitors

The development of safe, high energy and power electrochemical energy-conversion systems can be a response to the worldwide demand for a clean and low-fuel-consuming transport. This thesis work, starting from a basic studies on the ionic liquid (IL) electrolytes and carbon electrodes and concluding with tests on large-size IL-based supercapacitor prototypes demonstrated that the IL-based asymmetric configuration (AEDLCs) is a powerful strategy to develop safe, high-energy supercapacitors that might compete with lithium-ion batteries in power assist-hybrid electric vehicles (HEVs). The increase of specific energy in EDLCs was achieved following three routes: i) the use of hydrophobic ionic liquids (ILs) as electrolytes; ii) the design and preparation of carbon electrode materials of tailored morphology and surface chemistry to feature high capacitance response in IL and iii) the asymmetric double-layer carbon supercapacitor configuration (AEDLC) which consists of assembling the supercapacitor with different carbon loadings at the two electrodes in order to exploit the wide electrochemical stability window (ESW) of IL and to reach high maximum cell voltage (Vmax). Among the various ILs investigated the N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR1(2O1)TFSI) was selected because of its hydrophobicity and high thermal stability up to 350 °C together with good conductivity and wide ESW, exploitable in a wide temperature range, below 0°C. For such exceptional properties PYR1(2O1)TFSI was used for the whole study to develop large size IL-based carbon supercapacitor prototype. This work also highlights that the use of ILs determines different chemical-physical properties at the interface electrode/electrolyte with respect to that formed by conventional electrolytes. Indeed, the absence of solvent in ILs makes the properties of the interface not mediated by the solvent and, thus, the dielectric constant and double-layer thickness strictly depend on the chemistry of the IL ions. The study of carbon electrode materials evidences several factors that have to be taken into account for designing performing carbon electrodes in IL. The heat-treatment in inert atmosphere of the activated carbon AC which gave ACT carbon featuring ca. 100 F/g in IL demonstrated the importance of surface chemistry in the capacitive response of the carbons in hydrophobic ILs. The tailored mesoporosity of the xerogel carbons is a key parameter to achieve high capacitance response. The CO2-treated xerogel carbon X3a featured a high specific capacitance of 120 F/g in PYR14TFSI, however, exhibiting high pore volume, an excess of IL is required to fill the pores with respect to that necessary for the charge-discharge process. Further advances were achieved with electrodes based on the disordered template carbon DTC7 with pore size distribution centred at 2.7 nm which featured a notably high specific capacitance of 140 F/g in PYR14TFSI and a moderate pore volume, V>1.5 nm of 0.70 cm3/g. This thesis work demonstrated that by means of the asymmetric configuration (AEDLC) it was possible to reach high cell voltage up to 3.9 V. Indeed, IL-based AEDLCs with the X3a or ACT carbon electrodes exhibited specific energy and power of ca. 30 Wh/kg and 10 kW/kg, respectively. The DTC7 carbon electrodes, featuring a capacitance response higher of 20%-40% than those of X3a and ACT, respectively, enabled the development of a PYR14TFSI-based AEDLC with specific energy and power of 47 Wh/kg and 13 kW/kg at 60°C with Vmax of 3.9 V. Given the availability of the ACT carbon (obtained from a commercial material), the PYR1(2O1)TFSI-based AEDLCs assembled with ACT carbon electrodes were selected within the EU ILHYPOS project for the development of large-size prototypes. This study demonstrated that PYR1(2O1)TFSI-based AEDLC can operate between -30°C and +60°C and its cycling stability was proved at 60°C up to 27,000 cycles with high Vmax up to 3.8 V. Such AEDLC was further investigated following USABC and DOE FreedomCAR reference protocols for HEV to evaluate its dynamic pulse-power and energy features. It was demonstrated that with Vmax of 3.7 V at T> 30 °C the challenging energy and power targets stated by DOE for power-assist HEVs, and at T> 0 °C the standards for the 12V-TSS and 42V-FSS and TPA 2s-pulse applications are satisfied, if the ratio wmodule/wSC = 2 is accomplished, which, however, is a very demanding condition. Finally, suggestions for further advances in IL-based AEDLC performance were found. Particularly, given that the main contribution to the ESR is the electrode charging resistance, which in turn is affected by the ionic resistance in the pores that is also modulated by pore length, the pore geometry is a key parameter in carbon design not only because it defines the carbon surface but also because it can differentially “amplify” the effect of IL conductivity on the electrode charging-discharging process and, thus, supercapacitor time constant.

Milk and dairy products: evaluation of bioactive components by analytical techniques

Milk and dairy products are important source of bioactive compounds useful to satisfy the nutritional and physiological needs of any newborns of mammalian species and useful to guarantee adequate growth and development of infants as well as provide a complete nourishment of adults. Physico-chemical, nutritional and organoleptic properties of the main constituents and the “minor” components have a crucial role in the quality of milk and milk products. Although in the past decades dietary milk fat was often regarded as harmful for the human health, recent researches suggest that milk contains specific fatty acids with nutritional and physiological health benefits. For these reasons, a major attention is given to the quantity and quality of total fat intake. In the recent years, as a result of the new concept of multifunctional agriculture and the changing behaviours about diet, consumer demands in favor of high-quality, security and safety dairy products are increased. Moreover, milk proteins and milk-derived bioactive peptides are recognized to have a high nutritive value, several health-promoting functional activities and excellent technological properties. Accordingly, growing interest in the development of functional dairy products and preparation of infant formulae for babies who cannot be breast-fed, has been give in order to meet the specific consumer’s requests. This manuscript presents the main results obtained during my PhD research aimed to evaluate the main bioactive lipids and proteins in milk and dairy products using innovative analytical techniques. The experimental section of this manuscript is divided in two sections where are reported the main results obtained during my research activities on dairy products and human milks in order to characterize their bioactive compounds for functional food applications.

Dalla città alla casa, dalla casa alla città: la mutevole ricerca di un Piano per il ben-essere urbano

La ricerca si propone di definire le linee guida per la stesura di un Piano che si occupi di qualità della vita e di benessere. Il richiamo alla qualità e al benessere è positivamente innovativo, in quanto impone agli organi decisionali di sintonizzarsi con la soggettività attiva dei cittadini e, contemporaneamente, rende evidente la necessità di un approccio più ampio e trasversale al tema della città e di una più stretta relazione dei tecnici/esperti con i responsabili degli organismi politicoamministrativi. La ricerca vuole indagare i limiti dell’urbanistica moderna di fronte alla complessità di bisogni e di nuove necessità espresse dalle popolazioni urbane contemporanee. La domanda dei servizi è notevolmente cambiata rispetto a quella degli anni Sessanta, oltre che sul piano quantitativo anche e soprattutto sul piano qualitativo, a causa degli intervenuti cambiamenti sociali che hanno trasformato la città moderna non solo dal punto di vista strutturale ma anche dal punto di vista culturale: l’intermittenza della cittadinanza, per cui le città sono sempre più vissute e godute da cittadini del mondo (turisti e/o visitatori, temporaneamente presenti) e da cittadini diffusi (suburbani, provinciali, metropolitani); la radicale trasformazione della struttura familiare, per cui la famiglia-tipo costituita da una coppia con figli, solido riferimento per l’economia e la politica, è oggi minoritaria; l’irregolarità e flessibilità dei calendari, delle agende e dei ritmi di vita della popolazione attiva; la mobilità sociale, per cui gli individui hanno traiettorie di vita e pratiche quotidiane meno determinate dalle loro origini sociali di quanto avveniva nel passato; l’elevazione del livello di istruzione e quindi l’incremento della domanda di cultura; la crescita della popolazione anziana e la forte individualizzazione sociale hanno generato una domanda di città espressa dalla gente estremamente variegata ed eterogenea, frammentata e volatile, e per alcuni aspetti assolutamente nuova. Accanto a vecchie e consolidate richieste – la città efficiente, funzionale, produttiva, accessibile a tutti – sorgono nuove domande, ideali e bisogni che hanno come oggetto la bellezza, la varietà, la fruibilità, la sicurezza, la capacità di stupire e divertire, la sostenibilità, la ricerca di nuove identità, domande che esprimono il desiderio di vivere e di godere la città, di stare bene in città, domande che non possono essere più soddisfatte attraverso un’idea di welfare semplicemente basata sull’istruzione, la sanità, il sistema pensionistico e l’assistenza sociale. La città moderna ovvero l’idea moderna della città, organizzata solo sui concetti di ordine, regolarità, pulizia, uguaglianza e buon governo, è stata consegnata alla storia passata trasformandosi ora in qualcosa di assai diverso che facciamo fatica a rappresentare, a descrivere, a raccontare. La città contemporanea può essere rappresentata in molteplici modi, sia dal punto di vista urbanistico che dal punto di vista sociale: nella letteratura recente è evidente la difficoltà di definire e di racchiudere entro limiti certi l’oggetto “città” e la mancanza di un convincimento forte nell’interpretazione delle trasformazioni politiche, economiche e sociali che hanno investito la società e il mondo nel secolo scorso. La città contemporanea, al di là degli ambiti amministrativi, delle espansioni territoriali e degli assetti urbanistici, delle infrastrutture, della tecnologia, del funzionalismo e dei mercati globali, è anche luogo delle relazioni umane, rappresentazione dei rapporti tra gli individui e dello spazio urbano in cui queste relazioni si muovono. La città è sia concentrazione fisica di persone e di edifici, ma anche varietà di usi e di gruppi, densità di rapporti sociali; è il luogo in cui avvengono i processi di coesione o di esclusione sociale, luogo delle norme culturali che regolano i comportamenti, dell’identità che si esprime materialmente e simbolicamente nello spazio pubblico della vita cittadina. Per studiare la città contemporanea è necessario utilizzare un approccio nuovo, fatto di contaminazioni e saperi trasversali forniti da altre discipline, come la sociologia e le scienze umane, che pure contribuiscono a costruire l’immagine comunemente percepita della città e del territorio, del paesaggio e dell’ambiente. La rappresentazione del sociale urbano varia in base all’idea di cosa è, in un dato momento storico e in un dato contesto, una situazione di benessere delle persone. L’urbanistica moderna mirava al massimo benessere del singolo e della collettività e a modellarsi sulle “effettive necessità delle persone”: nei vecchi manuali di urbanistica compare come appendice al piano regolatore il “Piano dei servizi”, che comprende i servizi distribuiti sul territorio circostante, una sorta di “piano regolatore sociale”, per evitare quartieri separati per fasce di popolazione o per classi. Nella città contemporanea la globalizzazione, le nuove forme di marginalizzazione e di esclusione, l’avvento della cosiddetta “new economy”, la ridefinizione della base produttiva e del mercato del lavoro urbani sono espressione di una complessità sociale che può essere definita sulla base delle transazioni e gli scambi simbolici piuttosto che sui processi di industrializzazione e di modernizzazione verso cui era orientata la città storica, definita moderna. Tutto ciò costituisce quel complesso di questioni che attualmente viene definito “nuovo welfare”, in contrapposizione a quello essenzialmente basato sull’istruzione, sulla sanità, sul sistema pensionistico e sull’assistenza sociale. La ricerca ha quindi analizzato gli strumenti tradizionali della pianificazione e programmazione territoriale, nella loro dimensione operativa e istituzionale: la destinazione principale di tali strumenti consiste nella classificazione e nella sistemazione dei servizi e dei contenitori urbanistici. E’ chiaro, tuttavia, che per poter rispondere alla molteplice complessità di domande, bisogni e desideri espressi dalla società contemporanea le dotazioni effettive per “fare città” devono necessariamente superare i concetti di “standard” e di “zonizzazione”, che risultano essere troppo rigidi e quindi incapaci di adattarsi all’evoluzione di una domanda crescente di qualità e di servizi e allo stesso tempo inadeguati nella gestione del rapporto tra lo spazio domestico e lo spazio collettivo. In questo senso è rilevante il rapporto tra le tipologie abitative e la morfologia urbana e quindi anche l’ambiente intorno alla casa, che stabilisce il rapporto “dalla casa alla città”, perché è in questa dualità che si definisce il rapporto tra spazi privati e spazi pubblici e si contestualizzano i temi della strada, dei negozi, dei luoghi di incontro, degli accessi. Dopo la convergenza dalla scala urbana alla scala edilizia si passa quindi dalla scala edilizia a quella urbana, dal momento che il criterio del benessere attraversa le diverse scale dello spazio abitabile. Non solo, nei sistemi territoriali in cui si è raggiunto un benessere diffuso ed un alto livello di sviluppo economico è emersa la consapevolezza che il concetto stesso di benessere sia non più legato esclusivamente alla capacità di reddito collettiva e/o individuale: oggi la qualità della vita si misura in termini di qualità ambientale e sociale. Ecco dunque la necessità di uno strumento di conoscenza della città contemporanea, da allegare al Piano, in cui vengano definiti i criteri da osservare nella progettazione dello spazio urbano al fine di determinare la qualità e il benessere dell’ambiente costruito, inteso come benessere generalizzato, nel suo significato di “qualità dello star bene”. E’ evidente che per raggiungere tale livello di qualità e benessere è necessario provvedere al soddisfacimento da una parte degli aspetti macroscopici del funzionamento sociale e del tenore di vita attraverso gli indicatori di reddito, occupazione, povertà, criminalità, abitazione, istruzione, etc.; dall’altra dei bisogni primari, elementari e di base, e di quelli secondari, culturali e quindi mutevoli, trapassando dal welfare state allo star bene o well being personale, alla wellness in senso olistico, tutte espressioni di un desiderio di bellezza mentale e fisica e di un nuovo rapporto del corpo con l’ambiente, quindi manifestazione concreta di un’esigenza di ben-essere individuale e collettivo. Ed è questa esigenza, nuova e difficile, che crea la diffusa sensazione dell’inizio di una nuova stagione urbana, molto più di quanto facciano pensare le stesse modifiche fisiche della città.

Arbitrary Waveform Multilevel Generator for High Voltage High Frequency Plasma Actuators

This dissertation presents the theory and the conducted activity that lead to the construction of a high voltage high frequency arbitrary waveform voltage generator. The generator has been specifically designed to supply power to a wide range of plasma actuators. The system has been completely designed, manufactured and tested at the Department of Electrical, Electronic and Information Engineering of the University of Bologna. The generator structure is based on the single phase cascaded H-bridge multilevel topology and is comprised of 24 elementary units that are series connected in order to form the typical staircase output voltage waveform of a multilevel converter. The total number of voltage levels that can be produced by the generator is 49. Each level is 600 V making the output peak-to-peak voltage equal to 28.8 kV. The large number of levels provides high resolution with respect to the output voltage having thus the possibility to generate arbitrary waveforms. Maximum frequency of operation is 20 kHz. A study of the relevant literature shows that this is the first time that a cascaded multilevel converter of such dimensions has been constructed. Isolation and control challenges had to be solved for the realization of the system. The biggest problem of the current technology in power supplies for plasma actuators is load matching. Resonant converters are the most used power supplies and are seriously affected by this problem. The manufactured generator completely solves this issue providing consistent voltage output independently of the connected load. This fact is very important when executing tests and during the comparison of the results because all measures should be comparable and not dependent from matching issues. The use of the multilevel converter for power supplying a plasma actuator is a real technological breakthrough that has provided and will continue to provide very significant experimental results.

High performance and energy-efficient instruction cache design and optimisation for ultra-low-power multi-core clusters

High Energy efficiency and high performance are the key regiments for Internet of Things (IoT) end-nodes. Exploiting cluster of multiple programmable processors has recently emerged as a suitable solution to address this challenge. However, one of the main bottlenecks for multi-core architectures is the instruction cache. While private caches fall into data replication and wasting area, fully shared caches lack scalability and form a bottleneck for the operating frequency. Hence we propose a hybrid solution where a larger shared cache (L1.5) is shared by multiple cores connected through a low-latency interconnect to small private caches (L1). However, it is still limited by large capacity miss with a small L1. Thus, we propose a sequential prefetch from L1 to L1.5 to improve the performance with little area overhead. Moreover, to cut the critical path for better timing, we optimized the core instruction fetch stage with non-blocking transfer by adopting a 4 x 32-bit ring buffer FIFO and adding a pipeline for the conditional branch. We present a detailed comparison of different instruction cache architectures' performance and energy efficiency recently proposed for Parallel Ultra-Low-Power clusters. On average, when executing a set of real-life IoT applications, our two-level cache improves the performance by up to 20% and loses 7% energy efficiency with respect to the private cache. Compared to a shared cache system, it improves performance by up to 17% and keeps the same energy efficiency. In the end, up to 20% timing (maximum frequency) improvement and software control enable the two-level instruction cache with prefetch adapt to various battery-powered usage cases to balance high performance and energy efficiency.

High performance battery chargers for full electric and hybrid cars

This Doctoral Thesis aims to study and develop advanced and high-efficient battery chargers for full electric and plug-in electric cars. The document is strictly industry-oriented and relies on automotive standards and regulations. In the first part a general overview about wireless power transfer battery chargers (WPTBCs) and a deep investigation about international standards are carried out. Then, due to the highly increasing attention given to WPTBCs by the automotive industry and considering the need of minimizing weight, size and number of components this work focuses on those architectures that realize a single stage for on-board power conversion avoiding the implementation of the DC/DC converter upstream the battery. Based on the results of the state-of-the-art, the following sections focus on two stages of the architecture: the resonant tank and the primary DC/AC inverter. To reach the maximum transfer efficiency while minimizing weight and size of the vehicle assembly a coordinated system level design procedure for resonant tank along with an innovative control algorithm for the DC/AC primary inverter is proposed. The presented solutions are generalized and adapted for the best trade-off topologies of compensation networks: Series-Series and Series-Parallel. To assess the effectiveness of the above-mentioned objectives, validation and testing are performed through a simulation environment, while experimental test benches are carried out by the collaboration of Delft University of Technology (TU Delft).

Design and testing of innovative, artificial intelligence-based techniques to model and control the combustion process and to reduce the Co2 emissions in modern, high-performance, gasoline direct injection engines

This work deals with the development of calibration procedures and control systems to improve the performance and efficiency of modern spark ignition turbocharged engines. The algorithms developed are used to optimize and manage the spark advance and the air-to-fuel ratio to control the knock and the exhaust gas temperature at the turbine inlet. The described work falls within the activity that the research group started in the previous years with the industrial partner Ferrari S.p.a. . The first chapter deals with the development of a control-oriented engine simulator based on a neural network approach, with which the main combustion indexes can be simulated. The second chapter deals with the development of a procedure to calibrate offline the spark advance and the air-to-fuel ratio to run the engine under knock-limited conditions and with the maximum admissible exhaust gas temperature at the turbine inlet. This procedure is then converted into a model-based control system and validated with a Software in the Loop approach using the engine simulator developed in the first chapter. Finally, it is implemented in a rapid control prototyping hardware to manage the combustion in steady-state and transient operating conditions at the test bench. The third chapter deals with the study of an innovative and cheap sensor for the in-cylinder pressure measurement, which is a piezoelectric washer that can be installed between the spark plug and the engine head. The signal generated by this kind of sensor is studied, developing a specific algorithm to adjust the value of the knock index in real-time. Finally, with the engine simulator developed in the first chapter, it is demonstrated that the innovative sensor can be coupled with the control system described in the second chapter and that the performance obtained could be the same reachable with the standard in-cylinder pressure sensors.

Hypofractionated stereotactic radiotherapy after hyperbaric oxygenation for recurrent high-grade glioma: a pilot study

Purpose The presence of hypoxic cells in high-grade glioma (HGG) is one of the main reasons of local failure after radiotherapy (RT). The use of hyperbaric oxygen therapy (HBO) could help to overcome the problem of hypoxia in poorly oxygenated regions of the tumor. We performed a pilot study to evaluate the efficacy of hypofractionated image-guided helical TomoTherapy (HT) after HBO in the treatment of recurrent HGG (rHGG). Methods We enrolled 15 patients (aged >18 years) with diagnosis of rHGG. A total dose of 15-25 Gy was administered in daily 5-Gy fractions for 3-5 consecutive days after daily HBO. Each fraction was delivered up to maximum of 60 minutes after HBO. Results Median follow-up from HBO-RT was 28.6 (range: 5.3-56.8). No patient was lost to follow-up. Median progression-free survival (mPFS) for all patients was 3.2 months (95% CI: 1.34- 6.4 ), while 3-month, 6-month and 12 month PFS was 60% (95%CI: 31.8.4-79.7), 40% (95%CI: 16.5- 62.8) and10.0 (0.8-33.5) , respectively. Median overall survival (mOS) of HBO-RT was 11.7 months (95% CI: 7.3-29.3), while 3-month, 6-month and 12 month OS was 100% , 93.3% (61.3-99.0) and 46.7 % (21.2-68.8). No acute or late neurologic toxicity >grade 2 (CTCAE version 4.3) was observed in 86.66% of patients. Two patients developed G3 Radionecrosis. Conclusion HSRT combined to HBO seems effective and safe in the treatment of rHGG. One of advantages of HBO-RT is the reduced overall treatment time (3-5 consecutive days).