Analysis of Lead-Acid batteries with a third-order dynamical model

Electrical energy storage is a really important issue nowadays. As electricity is not easy to be directly stored, it can be stored in other forms and converted back to electricity when needed. As a consequence, storage technologies for electricity can be classified by the form of storage, and in particular we focus on electrochemical energy storage systems, better known as electrochemical batteries. Largely the more widespread batteries are the Lead-Acid ones, in the two main types known as flooded and valve-regulated. Batteries need to be present in many important applications such as in renewable energy systems and in motor vehicles. Consequently, in order to simulate these complex electrical systems, reliable battery models are needed. Although there exist some models developed by experts of chemistry, they are too complex and not expressed in terms of electrical networks. Thus, they are not convenient for a practical use by electrical engineers, who need to interface these models with other electrical systems models, usually described by means of electrical circuits. There are many techniques available in literature by which a battery can be modeled. Starting from the Thevenin based electrical model, it can be adapted to be more reliable for Lead-Acid battery type, with the addition of a parasitic reaction branch and a parallel network. The third-order formulation of this model can be chosen, being a trustworthy general-purpose model, characterized by a good ratio between accuracy and complexity. Considering the equivalent circuit network, all the useful equations describing the battery model are discussed, and then implemented one by one in Matlab/Simulink. The model has been finally validated, and then used to simulate the battery behaviour in different typical conditions.

Organic/inorganic polyoxometalate-based hybrids for oxidation catalysis and energy conversion

This thesis work has been carried out during the Erasmus exchange period at the “Université Paris 6 – Pierre et Marie Curie”, in the “Edifices PolyMétalliques – EPOM” team, leaded by Prof. Anna Proust, belonging to the “Institut Parisien de Chimie Moléculaire”, under the supervision of Dr. Guillaume Izzet and Dr. Geoffroy Guillemot. The redox properties of functionalized Keggin and Dawson POMs have been exploited in photochemical, catalytic and reactivity tests. For the photochemical purposes, the selected POMs have been functionalized with different photoactive FGs, and the resulting products have been characterized by CV analyses, luminescence tests and UV-Vis analyses. In future, these materials will be tested for hydrogen photoproduction and polymerization of photoactive films. For the catalytic purposes, POMs have been firstly functionalized with silanol moieties, to obtain original coordination sites, and then post-functionalized with TMs such as V, Ti and Zr in their highest oxidation states. In this way, the catalytic properties of TMs were coupled to the redox properties of POM frameworks. The redox behavior of some of these hybrids has been studied by spectro-electrochemical and EPR methods. Catalytic epoxidation tests have been carried out on allylic alcohols and n-olefins, employing different catalysts and variable amounts of them. The performances of POM-V hybrids have been compared to those of VO(iPrO)3. Finally, reactivity of POM-VIII hybrids has been studied, using styrene oxide and ethyl-2-diazoacetate as substrates. All the obtained products have been analyzed via NMR techniques. Cyclovoltammetric analyses have been carried out in order to determine the redox behavior of selected hybrids.

Electrochemical oxidation of Kraft and Dealkaline lignin to produce value-added chemicals on Nickel electrocatalysts

One of the most important scientific and environmental issues is reducing global dependence on fossil sources and one of the solutions is to use biomass as feedstock. In particular, the use of lignocellulosic biomass to obtain molecules with considerable commercial importance is gaining more and more interest. Lignin, the most recalcitrant part of lignocellulosic biomass, is a valuable source of sustainable and renewable aromatic molecules, currently produced from petrochemical processes. Vanillin, one of the most important aromatic aldehydes on an industrial level, can be obtained through catalytic lignin oxidation. An alternative to the conventional catalytic oxidation process is the electro-catalytic process, which can be carried out at ambient temperature and pressure, using water as solvent, and it can be considered as a renewable energy storage. In this thesis, the electrocatalytic oxidation of Kraft and Dealkaline lignin in NaOH was investigated over Ni foam catalysts. The effect of the reaction parameters (i.e. time, applied potential, lignin concentration, NaOH concentration, and temperature) on the yields of vanillin and other valuable products was evaluated. After the screening of the reaction conditions, a systematic study of the contribution of the homogeneous reaction (lignin depolymerization due to the basic solvent) to the yield of the product was accomplished. Finally, considering the obtained results, an alternative reaction procedure was proposed.