Big data analytics for proactive and predictive maintenance in electric car battery packs

The idea behind the project is to develop a methodology for analyzing and developing techniques for the diagnosis and the prediction of the state of charge and health of lithium-ion batteries for automotive applications. For lithium-ion batteries, residual functionality is measured in terms of state of health; however, this value cannot be directly associated with a measurable value, so it must be estimated. The development of the algorithms is based on the identification of the causes of battery degradation, in order to model and predict the trend. Therefore, models have been developed that are able to predict the electrical, thermal and aging behavior. In addition to the model, it was necessary to develop algorithms capable of monitoring the state of the battery, online and offline. This was possible with the use of algorithms based on Kalman filters, which allow the estimation of the system status in real time. Through machine learning algorithms, which allow offline analysis of battery deterioration using a statistical approach, it is possible to analyze information from the entire fleet of vehicles. Both systems work in synergy in order to achieve the best performance. Validation was performed with laboratory tests on different batteries and under different conditions. The development of the model allowed to reduce the time of the experimental tests. Some specific phenomena were tested in the laboratory, and the other cases were artificially generated.

Advanced lithium and lithium-ion rechargeable batteries for automotive applications

The worldwide demand for a clean and low-fuel-consuming transport promotes the development of safe, high energy and power electrochemical storage and conversion systems. Lithium-ion batteries (LIBs) are considered today the best technology for this application as demonstrated by the recent interest of automotive industry in hybrid (HEV) and electric vehicles (EV) based on LIBs. This thesis work, starting from the synthesis and characterization of electrode materials and the use of non-conventional electrolytes, demonstrates that LIBs with novel and safe electrolytes and electrode materials meet the targets of specific energy and power established by U.S.A. Department of Energy (DOE) for automotive application in HEV and EV. In chapter 2 is reported the origin of all chemicals used, the description of the instruments used for synthesis and chemical-physical characterizations, the electrodes preparation, the batteries configuration and the electrochemical characterization procedure of electrodes and batteries. Since the electrolyte is the main critical point of a battery, in particular in large- format modules, in chapter 3 we focused on the characterization of innovative and safe electrolytes based on ionic liquids (characterized by high boiling/decomposition points, thermal and electrochemical stability and appreciable conductivity) and mixtures of ionic liquid with conventional electrolyte. In chapter 4 is discussed the microwave accelerated sol–gel synthesis of the carbon- coated lithium iron phosphate (LiFePO 4 -C), an excellent cathode material for LIBs thanks to its intrinsic safety and tolerance to abusive conditions, which showed excellent electrochemical performance in terms of specific capacity and stability. In chapter 5 are presented the chemical-physical and electrochemical characterizations of graphite and titanium-based anode materials in different electrolytes. We also characterized a new anodic material, amorphous SnCo alloy, synthetized with a nanowire morphology that showed to strongly enhance the electrochemical stability of the material during galvanostatic full charge/discharge cycling. Finally, in chapter 6, are reported different types of batteries, assembled using the LiFePO 4 -C cathode material, different anode materials and electrolytes, characterized by deep galvanostatic charge/discharge cycles at different C-rates and by test procedures of the DOE protocol for evaluating pulse power capability and available energy. First, we tested a battery with the innovative cathode material LiFePO 4 -C and conventional graphite anode and carbonate-based electrolyte (EC DMC LiPF 6 1M) that demonstrated to surpass easily the target for power-assist HEV application. Given that the big concern of conventional lithium-ion batteries is the flammability of highly volatile organic carbonate- based electrolytes, we made safe batteries with electrolytes based on ionic liquid (IL). In order to use graphite anode in IL electrolyte we added to the IL 10% w/w of vinylene carbonate (VC) that produces a stable SEI (solid electrolyte interphase) and prevents the graphite exfoliation phenomenon. Then we assembled batteries with LiFePO 4 -C cathode, graphite anode and PYR 14 TFSI 0.4m LiTFSI with 10% w/w of VC that overcame the DOE targets for HEV application and were stable for over 275 cycles. We also assembled and characterized ―high safety‖ batteries with electrolytes based on pure IL, PYR 14 TFSI with 0.4m LiTFSI as lithium salt, and on mixture of this IL and standard electrolyte (PYR 14 TFSI 50% w/w and EC DMC LiPF 6 50% w/w), using titanium-based anodes (TiO 2 and Li 4 Ti 5 O 12 ) that are commonly considered safer than graphite in abusive conditions. The batteries bearing the pure ionic liquid did not satisfy the targets for HEV application, but the batteries with Li 4 Ti 5 O 12 anode and 50-50 mixture electrolyte were able to surpass the targets. We also assembled and characterized a lithium battery (with lithium metal anode) with a polymeric electrolyte based on poly-ethilenoxide (PEO 20 – LiCF 3 SO 3 +10%ZrO 2 ), which satisfied the targets for EV application and showed a very impressive cycling stability. In conclusion, we developed three lithium-ion batteries of different chemistries that demonstrated to be suitable for application in power-assist hybrid vehicles: graphite/EC DMC LiPF 6 /LiFePO 4 -C, graphite/PYR 14 TFSI 0.4m LiTFSI with 10% VC/LiFePO 4 -C and Li 4 T i5 O 12 /PYR 14 TFSI 50%-EC DMC LiPF 6 50%/LiFePO 4 -C. We also demonstrated that an all solid-state polymer lithium battery as Li/PEO 20 –LiCF 3 SO 3 +10%ZrO 2 /LiFePO 4 -C is suitable for application on electric vehicles. Furthermore we developed a promising anodic material alternative to the graphite, based on SnCo amorphous alloy.

Towards eco-friendly batteries: concepts for lithium and sodium ion batteries

Several possibilities are arising aiming the development of “greener”, more sustainable energy storage systems. One point is the completely water-based processing of battery electrodes, thus being able to renounce the use of toxic solvents in the preparation process. Despite its advantage of lower cost and eco-friendlyness, there is the need of similar mechanical and electrochemichal behavior for boosting this preparation mode. Another point – accompanying the water-based processing - is the replacement of solvent-based polymer binders by water-based ones. These binders can be based on fluorinated, crude-oil based polymers on the one side, but also on naturally abundant and economic friendly biopolymers. The most common anode materials, graphite and lithium titanate (LTO), have been subjected a water-based preparation route with different binder systems. LTO is a promising anode material for lithium ion batteries (LIBs), as it shows excellent safety characteristics, does not form a significant SEI and its volume change upon intercalation of lithium ions is negligible. Unfortunately, this material suffers from a rather low electric conductivity - that is why an intensive study on improved current collector surfaces for LTO electrodes was performed. In order to go one step ahead towards sustainable energy storage, anode and cathode active materials for a sodium ion battery were synthesized. Anode active material resulted in a successful product which was then subjected to further electrochemical tests. In this PhD work the development of “greener” energy storage possibilities is tested under several aspects. The ecological impact of raw materials and required battery components is examined in detail.

Synthesis and characterization of prussian blue analogue materials for post-Li ion batteries

Energy issues have always been a subject of concern to people. During the past 30 years, rechargeable Li-ion batteries (LIBs) have been widely used in portable electronic devices and power tools because of their high energy density and efficiency among practical secondary batteries. While the unevenly distribution of Lithium sources and the increasing cost of lithium-raw material can not satisfy the requirement for further cost reduction, especially for the grid-scale energy storage. Post-lithium ion batteries as promising replacement for LIBs have attracted wide attention, owing to their high abundant resources and adequate insertion potential. Similar with Li-ion batteries, finding a suitable electrode material is the key for the research and application of the post-Li ion batteries. In our project, we focus our study on Prussian blue analogues (PBAs), with formula AxM[M’(CN)6]1-y□y•zH2O (0≤x≤2, 0batteries. The most commonly studied PBAs are metal haxacyanoferrate, with the carbon-sites of -CN- ligands fix connected with Fe. Here, we synthesized three different PBAs: manganese hexacynoferrate (MnHCF), zinc hexacynoferrate (ZnHCF) and titanium hexacynoferrate (TiHCF), using co-precipitation method, and their electrochemical properties were tested in both aqueous Na+, K+, Mg2+, Zn2+ and organic Li+, Na+ electrolytes. Various X-ray techniques were employed to study their electronic and structural properties of electrodes and electrochemical reaction mechanism during cycling.

In-car sound linear simulation

In recent years, vehicle acoustics have gained significant importance in new car development: increasingly advanced infotainment systems for spatial audio and sound enhancement algorithms have become the norm in modern vehicles. In the past, car manufacturers had to build numerous prototypes to study the sound behaviour inside the car cabin or the effect of new algorithms under development. Nowadays, advanced simulation techniques can reduce development costs and time. In this work, after selecting the reference test vehicle, a modern luxury sedan equipped with a high-end sound system, two independent tools were developed: a simulation tool created in the Comsol Multiphysics environment and an auralization tool developed in the Cycling ‘74 MAX environment. The simulation tool can calculate the impulse response and acoustic spectrum at a specific position inside the cockpit. Its input data are the vehicle’s geometry, acoustic absorption parameters of materials, the acoustic characteristics and position of loudspeakers, and the type and position of virtual microphones (or microphone arrays). The simulation tool can also provide binaural impulse responses thanks to Head Related Transfer Functions (HRTFs) and an innovative algorithm able to compute the HRTF at any distance and angle from the head. Impulse responses from simulations or acoustic measurements inside the car cabin are processed and fed into the auralization tool, enabling real-time interaction by applying filters, changing the channels gain or displaying the acoustic spectrum. Since the acoustic simulation of a vehicle involves multiple topics, the focus of this work has not only been the development of two tools but also the study and application of new techniques for acoustic characterization of the materials that compose the cockpit and the loudspeaker simulation. Specifically, three different methods have been applied for material characterization through the use of a pressure-velocity probe, a Laser Doppler Vibrometer (LDV), and a microphone array.

Analysis of efficacy and safety of CAR T-cell therapy in relapsed/refractory lymphomas: current indications and future perspectives

In the last few years, the introduction of chimeric antigen receptor (CAR) T-cell therapy into clinical practice has revolutionized the approach to patients with relapsed/refractory (R/R) large B-cell lymphoma (LBCL), whose outcome used to be dismal with median overall survival (OS) of approximately 6 months with standard salvage therapy. At our Institute, we started treating diffuse large B-cell lymphoma (DLBCL) patients with CAR T-cell products in August 2019 and they received either axicabtagene ciloleucel (axi-cel) and tisagenlecleucel (tisa-cel) as per regulatory indications. This research project presents the 2-year follow-up of the first 53 treated patients. Our first aim is to investigate the feasibility of this treatment strategy in a real-world setting, although the reimbursement criteria set by the Italian Medicines Agency (Agenzia Italiana del Farmaco, AIFA) are very similar to the inclusion criteria of clinical trials and stricter than those established by the regulatory authorities of many foreign countries. One month after infusion, the ORR was 66% with 19 patients already in CR (38%). Restaging at 3, 6 and 12 months post-infusion shows that early CRs tend to be maintained over time and, moreover, that a considerable number of PRs and a few SDs can improve into a CR. The safety data were consistent with what is reported in the literature; toxicity was generally manageable, largely due to the increasing expertise in handling the specific adverse events related to CAR T-cell therapy. Our results confirms that CAR T-cell therapy is both safe and effective in a real-life setting and that it represents a crucial weapon in a subset of patients who were previously doomed to an inevitably severe prognosis.