Romano Giglioli’s research while affiliated with University of Pisa and other places

A panel of ionic liquids has been synthesized and their effect on the vanadyl acetylacetonate solubility in acetonitrile has been firstly assessed. 1-Butyl-3-methylimidazolium acetate showed an unprecedented result, increasing the VO(acac)2 solubility in acetonitrile of more than one magnitude order (from 0.06 M to 1.1 M) opening new interesting horizons for the possible applications of this vanadium complex. The electrochemical effect of the considered ionic liquids has been subsequently investigated through cyclic voltammetry and linear sweep voltammetry with rotating disk electrode, determining diffusion coefficient and kinetic current of VO(acac)2 in the considered media. In order to achieve a deeper understanding on the examined systems, VO(acac)2 solutions in acetonitrile ILs were eventually studied through IR, UV-Vis, and EPR spectroscopies, finding evidences, corroborated by DFT studies, of the formation of strong adducts between VO(acac)2 and ILs.

Reaching universal access to electricity by 2030 requires a massive deployment of mini-grids in rural areas of developing countries. Among the many challenges hindering this process, there are the high uncertainties in assessing demand patterns in rural communities, the costs of field survey campaigns, and the absence of ample and reliable datasets coming from existing projects. This paper tries to address these issues by presenting and discussing a database of load profiles from sixty-one off-grid mini-grids from developing countries worldwide, gathered from the literature, private developers and fieldworks, and reported with technical, socio-economic and geographical characterization factors. A clustering procedure led to the identification of five archetypal load profile clusters, which are presented and analyzed together with their load duration curves. Subsequently, the distribution among the clusters of the various characterization factors selected is studied. The proposed approach allows to widen the range of load profiles usually considered, and to seek correlations between the load profile shapes, the peak power and average energy consumption per connection, the number of customers, the age of measurement, geographical position, operator model, type of tariff and generation technologies present. This work establishes a first step in the creation of a shared database for load profiles of rural mini-grids, helping to overcome the lack of available data and difficulties of demand assessment, proposing original insights for researchers to understand load patterns, and contributing to reduce risks and uncertainties for mini-grid developers.

In the framework of a scenario with an always increasing share of generation from variable renewable sources, the need for systems able to store energy or to convert the excess generation into useful goods is becoming of paramount importance. While several projects and pilot plants deal with direct energy storage or with the conversion of the excess generation into other energetic goods (hydrogen or methane) often overlooking economic considerations, this paper proposes a cost-effective approach in which liquified methane and oxygen are produced and sold on their specific markets, which represents one of the first profitable Power-to-X applications at current market values. The paper presents the completely new and never investigated before idea of coupling the plant with a freely available source of pure carbon dioxide from a geothermal unit, thus making it possible to produce synthetic methane to be liquefied, stored and then used in other sectors of the society. The carbon dioxide coming with the geothermal fluid is no longer released in the environment as it currently naturally happens even when not going through the geothermal facility. Detailed models of the main system components were created, and an optimization procedure was carried out. Interestingly, the revenues from the sale of liquefied oxygen are well above those coming from synthetic methane and turn the system profitable. With a proper operation planning, bidding on the electricity day-ahead-market, a large hydrogen storage system proved to be unnecessary. The results of the system optimization clearly show that this kind of systems, although conceived in a very favourable condition, can become profitable only if the energy storage function is coupled with the production of other goods services. Assuming an average electricity price of 52 €/MWh, the plant profitability is achieved for an LNG selling price of 0.45 €/kg and an LOx price around 0.30 €/kg. These figures will rapidly decrease in the near future as lower electricity prices are forecasted.

Tramway systems are more and more diffused today, to reduce pollution and greenhouse emissions. However, their electrical feeding substations can have significant margin for improvement. Therefore, it is questionable which kind of changes can be introduced, by changing their main features. First of all, transformer technology can be enhanced, by moving from the standard transformer to the amorphous metal one; thus, guaranteeing a significant reduction in losses. Then, by installing one dedicated storage systems for each substation. This solution can help to increase the energy efficiency; thus, recovering the tram braking energy and reducing the delivered energy from the grid, and also the reliability of the system; thus, guarantee different levels of services, in the case of failure of a feeding substation. This paper investigates in a systematic approach the two proposed solutions. In particular an amorphous metal transformer has been properly designed, and performance compared to the standard one. Then, evaluation of distributed storage installation was performed, and the aspects of reliability for these systems evaluated. Results have shown the general feasibility of the proposed solutions, showing a significant energy saving with respect to the conventional ones.

Dataset of beyond 60 load profiles from microgrids in developing countries, including socio-economic, weather and geographical data and clustering analyses

The paper proposes an innovative scheme exploiting oxygen liquefaction as a means for storing excess electricity generation from renewable sources. Liquid oxygen is then used in an oxy-combustion process with LNG to generate electricity when renewable energy generation is below the demand. An equivalent round trip efficiency is defined to make it possible comparing the system performances with hybrid plants including conventional generation and storage. The proposed scheme exhibits very high equivalent round trip efficiency, giving the system operators the opportunity to integrate more and more renewable energy generation inside power systems. Liquefied carbon dioxide and water are byproducts of the process. The size of the plant and of the storage tanks needed for a 4 TWh yearly demand with a peak around 800 MW is compatible with state-of-the-art systems used for LNG storage in similar size gas power plants.

To reduce the pollutant emissions in the naval sector, the use of alternative fuels and new power generator systems are both promising solutions. In this study, the feasibility of replacing a pleasure boat Auxiliary Power Unit (APU) with a hybrid solution is studied from the economic and technical points of view. Several power generation technologies and layouts are considered. Many configurations were investigated, from hybrid battery/diesel generator to innovative layouts including fuel cell with onboard Liquified Natural Gas (LNG) reforming for hydrogen production. Since hybrid APUs may yield significant advantages in terms of both environmental and noise pollution, the opportunity of operating the system for several hours without powering up the traditional generators is also considered. For each configuration, CO2 and NOx emissions, purchasing and operating costs, as well as weight and volume, are estimated. Emissions may be reduced up to 20 % and 60 % for CO2 and NOx, respectively, and fuel cost reductions up to 35 % may be achieved.

Vanadium redox flow battery (VRFB) is one of the most promising large-scale energy storage system; however, a widespread VRFB development is still limited by the poor electrochemical activity of graphite electrodes and a poor understanding of redox reactions occurring at electrode/electrolyte interface. In this work, DFT was performed to study the first solvation shell structure of all vanadium ions and to investigate the reactivity of modified graphite electrodes toward the V2+/V3+ redox species. The results suggest that the presence of oxygen and nitrogen functionalities at the electrode edges provides more active sites for adsorption of the V2+/V3+ redox couple, and therefore improve electron transfer kinetics. These results have been experimentally validated by means of Cyclic Voltammetry and Electrochemical. Impedance Spectroscopy with carbon black electrode having different density of oxygen and nitrogen-containing surface groups.

Vanadium redox flow battery(VRFB) is one of the most promising large- scale energy storage system; however, a wide spread VRFB development is still limited by the poor electrochemical activity of graphite electrodes and a poor understanding of redox reactions occurring at electrode /electrolyte interface. In this work, DFT was performed to study the first solvation shell structure of all vanadium ions and to investigate the reactivity of modified graphite electrodes toward the V2+/V3+ redox species.The results suggest that the presence of oxygen and nitrogen functionalities at the electrode edges provides more active sites for adsorption of the V2+/V3+ redox couple, and therefore improve electron transfer kinetics. These results have been experimentally validated by means of Cyclic Voltammetry and Electrochemical Impedance Spectroscopy with carbon black electrode having different density of oxygen and nitrogen-containing surface groups

In order to successfully deploy a large number of decentralized energy systems in developing countries, it is necessary to standardize effective methodologies and procedures to develop off-grid/mini-grid systems. Considering that the energy need assessment provides inputs and assumptions used in business modelling and mini-grid design, the accuracy of its results directly affects the technical and financial feasibility studies. Thus, the approach for applying a proven methodology for the energy need assessment of rural communities is aimed at obtaining reliable input data for the mini-grid development. This helps in reducing both the financial challenges by mitigating the uncertainties in electricity demand and the technical challenges by contributing to adequately size off-grid power generation systems, with a view to boost toward a common overall objective of mini-grid's optimization methods and tools. Hence, taking into consideration that target communities differ in terms of needs and context conditions, the proposed paper describes an inclusive methodology that can be adapted case-by-case. It provides an effective applied solution the lack of proven guidelines from project developers or literature, giving priority to data collection methods able to achieve a large sample representative of the market, with high accuracy in estimating the energy consumptions from electricity substitutes.