Graphite for lithium-ion batteries: mineral analysis and global Material Flow Analysis

Graphite is a mineral commodity used as anode for lithium-ion batteries (LIBs), and its global demand is doomed to increase significantly in the future due to the forecasted global market demand of electric vehicles. Currently, the graphite used to produce LIBs is a mix of synthetic and natural graphite. The first one is produced by the crystallization of petroleum by-products and the second comes from mining, which causes threats related to pollution, social acceptance, and health. This MSc work has the objective of determining compositional and textural characteristics of natural, synthetic, and recycled graphite by using SEM-EDS, XRF, XRD, and TEM analytical techniques and couple these data with dynamic Material Flow Analysis (MFA) models, which have the objective of predicting the future global use of graphite in order to test the hypothesis that natural graphite will no longer be used in the LIB market globally. The mineral analyses reveal that the synthetic graphite samples contain less impurities than the natural graphite, which has a rolled internal structure similar to the recycled one. However, recycled graphite shows fractures and discontinuities of the graphene layers caused by the recycling process, but its rolled internal structure can help the Li-ions’ migration through the fractures. Three dynamic MFA studies have been conducted to test distinct scenarios that include graphite recycling in the period 2022-2050 and it emerges that - irrespective of any considered scenario - there will be an increase of synthetic graphite demand, caused by the limited stocks of battery scrap available. Hence, I conclude that both natural and recycled graphite is doomed to be used in the LIB market in the future, at least until the year 2050 when the stock of recycled graphite production will be enough to supersede natural graphite. In addition, some new improvement in the dismantling and recycling processes are necessary to improve the quality of recycled graphite.

Valutazione del ciclo antropogenico del neodimio in Italia, mediante metodologie MFA e LCA

Per raggiungere gli obiettivi di neutralità climatica del 2050 stabiliti dal Green Deal europeo, l’approvvigionamento sicuro e sostenibile di materie prime critiche è considerato essenziale e l’attuale crisi energetica ne ha rimarcato l’importanza. Tra queste materie prime, il neodimio risulta essere fondamentale per un ampio numero di applicazioni tecnologiche di interesse crescente come la mobilità elettrica e la generazione di energia elettrica da fonti rinnovabili. La produzione mondiale di neodimio è dominata dalla Cina e l’Italia dipende completamente dalle importazioni per soddisfare la propria domanda. Il riciclo dei prodotti a fine vita potrebbe coprire parte della domanda nazionale di neodimio e ridurre la dipendenza dalle importazioni cinesi. Ma, attualmente, la percentuale di riciclo del metallo è inferiore all’1% globalmente con attività di riciclo spesso inesistenti su scala industriale a livello nazionale. Per dare chiarezza sulla catena del valore di neodimio in Italia e dimostrare le potenzialità del suo riciclo, in questa tesi sono state applicate le metodologie di MFA e di LCA. Un modello dinamico retrospettivo di MFA è stato sviluppato col fine di investigare il ciclo antropogenico del neodimio, identificando e valutando i flussi e le riserve nazionali dal 1995 al 2020. Attraverso un modello di distribuzione dei tempi di vita è stata quantificata la riserva in uso del metallo, che ammonta a 3,3 kt Nd o 56 g Nd pro capite. Un riciclo della riserva in uso potrebbe soddisfare l’attuale domanda di neodimio oltre al 2030. I risultati dell’MFA sono stati integrati con i fattori LCA di caratterizzazione di impatto ambientale, dimostrando che il riciclo potrebbe ridurre più dell’80% delle emissioni di gas serra e della energia richiesta associate alla produzione di neodimio primario. Si prevede che lo studio possa contribuire all’implementazione di politiche e strategie di rafforzamento della catena di approvvigionamento del neodimio.

Waste management in Forlì-Cesena province: Life Cycle Assessment (LCA) of Forlì incinerator

This work assesses the environmental impact of a municipal solid waste incinerator with energy recovery in Forlì-Cesena province (Emilia-Romagna region, Italy). The methodology used is Life Cycle Assessment (LCA). As the plant already applies the best technologies available in waste treatment, this study focuses on the fate of the residues (bottom and fly ash) produced during combustion. Nine scenarios are made, based on different ash treatment disposing/recycling techniques. The functional unit is the amount of waste incinerated in 2011. Boundaries are set from waste arrival in the plant to the disposal/recovery of the residues produced, with energy recovery. Only the operative period is considered. Software used is GaBi 4 and the LCIA method used is CML2001. The impact categories analyzed are: abiotic depletion, acidification, eutrophication, freshwater aquatic ecotoxicity, global warming, human toxicity, ozone layer depletion, photochemical oxidant formation, terrestrial ecotoxicity and primary energy demand. Most of the data are taken from Herambiente. When primary data are not available, data from Ecoinvent and GaBi databases or literature data are used. The whole incineration process is sustainable, due to the relevant avoided impact given by co-generator. As far as regards bottom ash treatment, the most influential process is the impact savings from iron recovery. Bottom ash recycling in road construction or as building material are both valid alternatives, even if the first option faces legislative limits in Italy. Regarding fly ash inertization, the adding of cement and Ferrox treatment results the most feasible alternatives. However, this inertized fly ash can maintain its hazardous nature. The only method to ensure the stability of an inertized fly ash is to couple two different stabilization treatments. Ash stabilization technologies shall improve with the same rate of the flexibility of the national legislation about incineration residues recycling.

The contribution of the Finite Volume Point Dilution Method to the determination of solute mass flux in an alluvial aquifer.

Groundwater represents one of the most important resources of the world and it is essential to prevent its pollution and to consider remediation intervention in case of contamination. According to the scientific community the characterization and the management of the contaminated sites have to be performed in terms of contaminant fluxes and considering their spatial and temporal evolution. One of the most suitable approach to determine the spatial distribution of pollutant and to quantify contaminant fluxes in groundwater is using control panels. The determination of contaminant mass flux, requires measurement of contaminant concentration in the moving phase (water) and velocity/flux of the groundwater. In this Master Thesis a new solute flux mass measurement approach, based on an integrated control panel type methodology combined with the Finite Volume Point Dilution Method (FVPDM), for the monitoring of transient groundwater fluxes, is proposed. Moreover a new adsorption passive sampler, which allow to capture the variation of solute concentration with time, is designed. The present work contributes to the development of this approach on three key points. First, the ability of the FVPDM to monitor transient groundwater fluxes was verified during a step drawdown test at the experimental site of Hermalle Sous Argentau (Belgium). The results showed that this method can be used, with optimal results, to follow transient groundwater fluxes. Moreover, it resulted that performing FVPDM, in several piezometers, during a pumping test allows to determine the different flow rates and flow regimes that can occurs in the various parts of an aquifer. The second field test aiming to determine the representativity of a control panel for measuring mass flus in groundwater underlined that wrong evaluations of Darcy fluxes and discharge surfaces can determine an incorrect estimation of mass fluxes and that this technique has to be used with precaution. Thus, a detailed geological and hydrogeological characterization must be conducted, before applying this technique. Finally, the third outcome of this work concerned laboratory experiments. The test conducted on several type of adsorption material (Oasis HLB cartridge, TDS-ORGANOSORB 10 and TDS-ORGANOSORB 10-AA), in order to determine the optimum medium to dimension the passive sampler, highlighted the necessity to find a material with a reversible adsorption tendency to completely satisfy the request of the new passive sampling technique.

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.

Optimal energy management of smart households with electric vehicles, energy storage and distributed generation

In this thesis, the optimal operation of a neighborhood of smart households in terms of minimizing the total energy cost is analyzed. Each household may comprise several assets such as electric vehicles, controllable appliances, energy storage and distributed generation. Bi-directional power flow is considered for each household . Apart from the distributed generation unit, technological options such as vehicle-to-home and vehicle-to-grid are available to provide energy to cover self-consumption needs and to export excessive energy to other households, respectively.

Steel hopper silos filled with granular material: experimental tests on the tensile resistance of corrugated sheets and on the filling and discharging pressures

This thesis addresses various aspects related to silos, from the strength of some structural parts to internal actions due to grain. Two hopper silo models were mainly studied, so the thesis is divided into two parts. The first part focuses only on the silo cylinder and deals with the collapse of a silo due to failure of the vertical walls. We had the opportunity to access data from a real silo and perform tensile tests on corrugated sheets. The theoretical and experimental resistance of the corrugated sheet forming the silo cylinder was studied. The resistance was then compared with the internal actions due to grain prescribed by various standards. The second part, however, focused on the hopper of a silo in which a load test (loading and unloading of the silo) was performed. Through the test data, an attempt was made to reproduce the pressures normal to the hopper through analytical reasoning. The experimental pressures were then compared with the theoretical pressures predicted by the standards. In addition, with mathematical reasoning, an attempt was made to reproduce the horizontal pressure on the vertical walls of the silo from the experimental normal pressure in the hopper. In fact, the test was related only to the hopper part and not to the silo cylinder.

Design and management of a supply chain: a joint location-inventory problem under uncertainty (Part B)

In recent years, global supply chains have increasingly suffered from reliability issues due to various external and difficult to-manage events. The following paper aims to build an integrated approach for the design of a Supply Chain under the risk of disruption and demand fluctuation. The study is divided in two parts: a mathematical optimization model, to identify the optimal design and assignments customer-facility, and a discrete-events simulation of the resulting network. The first one describes a model in which plant location decisions are influenced by variables such as distance to customers, investments needed to open plants and centralization phenomena that help contain the risk of demand variability (Risk Pooling). The entire model has been built with a proactive approach to manage the risk of disruptions assigning to each customer two types of open facilities: one that will serve it under normal conditions and a back-up facility, which comes into operation when the main facility has failed. The study is conducted on a relatively small number of instances due to the computational complexity, a matheuristic approach can be found in part A of the paper to evaluate the problem with a larger set of players. Once the network is built, a discrete events Supply Chain simulation (SCS) has been implemented to analyze the stock flow within the facilities warehouses, the actual impact of disruptions and the role of the back-up facilities which suffer a great stress on their inventory due to a large increase in demand caused by the disruptions. Therefore, simulation follows a reactive approach, in which customers are redistributed among facilities according to the interruptions that may occur in the system and to the assignments deriving from the design model. Lastly, the most important results of the study will be reported, analyzing the role of lead time in a reactive approach for the occurrence of disruptions and comparing the two models in terms of costs.