Comparison of incineration and pyrolysis of NMC-lithium-ion batteries – determination of the effects on the chemical composition, and potential formation of hazardous by-products.

Several industrial lithium battery recycling processes use thermal pre-treatment in an oxidative or inert atmosphere, or in a vacuum, to separate the battery components and remove organic material. However, a comparison of these pre-treatments on the microstructure and composition of waste material and production scrap LiBs has not been explored as well as there is a scarcity of information about the character of by-products generated during the processing.In this work the effects of incineration and dynamic pyrolysis on the composition of spent Li-ion batteries (LiBs) and the effects of incineration, dynamic pyrolysis, and pyrolysis under vacuum on the composition of production scrap Li-ion batteries (LiBs) were investigated. LiBs with cathode active material based on Li(NixMnyCoz)Oj, i.e. NMC-LiBs, were treated from 15 to 180 minutes at a temperature between 400-700\ub0C. During the pyrolysis, reactions with C and CO(g) led to a reduction of metal oxides, with Co, CoO, Ni, NiO, Mn, Mn3O4, Li2O, and Li2CO3 as the main products. During the incineration, the organic material was removed more efficiently than in pyrolysis and the lithium metal oxides were subjected to both carbothermic reduction and oxidation. During pyrolysis at 700\ub0C for 180 minutes, the carbon content decreased to 15w%, in comparison to the initial 41w%. The incineration performed under the same conditions resulted in almost complete removal of the graphite and organic species, ~0.6w%. Gas and organic oil by-products from the decomposition of the organic components were characterized. The presence of HF was detected and fluorine was identified also in the oil by-products. The decomposition of the binder facilitated the separation by mechanical treatment of the active material from the current collector. The best method to recover cathode material was shown to be incineration at a temperature range between 550˚ and 650˚ C for at least 90 minutes, followed by ball milling. The recovered fraction of active material was >95%.The formation of HF in the case of high temperature accident involving NMC-LiB was also determined. Four commercial refrigeration liquids containing halogens were investigated. The presence of these refrigeration liquids leads to an increase of the quantity of HF released during a simulated fire

La responsabilità di proteggere: evoluzione dell’intervento umanitario o una nuova modalità di protezione dei diritti umani?

La responsabilità di proteggere fin dal rapporto iniziale della Commissione Internazionale sulla Sovranità degli Stati, istituita dal Canada nel 2001, ha alimentato il dibattito tra gli Stati che sostengono la responsabilità di proteggere e gli Stati in via di sviluppo che ne subiscono l'azione. Inoltre sono stati presi in esame l'intervento della Comunità internazionale in Libia e il non intervento in Siria, evidenziando come l'applicazione della responsabilità di proteggere è condizionata a elementi di geopolitica che ne determinano l'applicazione. Interessante infine le posizione dei paesi del gruppo dei BRIC

Effects of pyrolysis and incineration on the chemical composition of Li-ion batteries and analysis of the by-products.

In the present work, the effects of pyrolysis and incineration on the composition of Li-ion battery cell materials and their dependence on treatment time and temperature were investigated. Waste from Li-ion batteries was treated at 400˚, 500˚, 600˚, and 700˚C for 30, 60, and 90 minutes. Thermodynamic calculations for the carbothermic reduction of the active materials LiCoO2, LiMn2O4, and LiNiO2 by graphite and the gas products were performed, and the results compared with the experimental data obtained by processing the pure oxides. This allowed for a very exact investigation of the behaviour of the oxides and has brought novel knowledge to the processing of Li-ion batteries. Moreover, to determine the behaviour of the real waste, NMC cathode material recovered from spent Li-ion batteries was studied. The results indicate that the organic compounds and the graphite are oxidized, by oxygen from the active material during the pyrolysis, and during incineration by the oxygen in the air present in the system, forming an atmosphere rich in CO(g) and CO2(g). Removal of the organic components increases the purity of the metal-bearing material. During the pyrolysis, reactions with C and CO(g) led to a reduction of metal oxides, with Co, CoO, Ni, NiO, Mn, Mn3O4, Li2O, and Li2CO3 as the main products. The reduction reactions transformed the metal compounds in the untreated LiB black mass into chemical forms that were more soluble. It was concluded that pyrolysis can be used as an effective tool for pre-treatment of battery waste in order to increase the efficiency of leaching in a hydrometallurgical processing of the black mass. During incineration, it was observed that the organic material was removed more efficiently than in pyrolysis and the lithium metal oxides were subjected to both carbothermic reduction and oxidation. During heat treatment, organic by-products were formed by the decomposition of the polypropylene separator and the PVDF binder. The organic residue contained both non-polar and polar compounds. One of the most important outputs of the current work is the observation of the fluorine behaviour during the thermal treatment, and detection of its presence in the oil product. It was shown that the decomposition of the PVDF facilitates the separation of the active material from the metallic layers of the electrodes by means of a mechanical treatment. An almost complete recovery of the black mass from the foils was achieved following the thermal treatment.\ua0 The results obtained can help to optimize the parameters in the industrial process that is already used for Li-ion battery recycling, since this research provides novel information about the effects of the thermal treatment and defines the most favourable conditions for the processing. The results could contribute to an increased recycling rate, especially if this process is followed by a hydrometallurgical treatment. Such optimization will decrease the energy demand and increase the metal recovery rate and the utilization of the by-products

Microwave gas sensor based on graphene aerogel for breath analysis

Exhaled breath can be used for early detection and diagnosis of diseases, monitoring metabolic activity, and precision medicine. In this work, we design and simulate a microwave sensor in which thin graphene aerogels are integrated into rectangular microwave waveguides. Graphene aerogels are ideal sensing platforms for gases and volatile compounds as they combine extremely high surface-to-volume ratio and good electrical conductivity at RF and microwave frequencies. The latter is modified by exposure to different gases, and -when integrated into a waveguide- these changes result in significant shifts in transmission and reflection scattering parameters. We model the aerogel as a graphene grid with hexagonal openings of size 22.86×10.16×0.1 mm3, characterized by an air volume equal to about 90 % of its entire volume. This grid is used as a building block for modeling thicker samples (up to 9 mm), To simulate the variation in the dynamic conductivity of the graphene sheets as a consequence of the absorption of gaseous molecules, a sweep of the chemical potential from 0.0 e V to 0.5 e V with steps of 0.1 e V was used. The results show a significant variation of the waveguide transmission scattering parameters resulting from the gas-induced modification of the graphene conductivity, and hence the potential of the proposed sensor design for breath analysis

S6: a Smart, Social and SDN-based Surveillance System for Smart-cities

Abstract In the last few years, Software Defined Networks (SDN) and Network Functions Virtualization (NFV) have been introduced in the Internet as a new way to design, deploy and manage networking services. Working together, they are able to consolidate and deliver the networking components using standard IT virtualization technologies not only on high-volume servers, but also in end user premises, Telco operator edge and access nodes thus allowing the emergence of new services. In this context, this paper presents a smart video surveillance platform designed to exploit the facilities offered by full SDN-NFV networks. This platform is based on free and open source software running on Provider Equipment (PE), so allowing function deployment simplification and management cost reduction

Earthquake-triggered landslide susceptibility in Italy by means of Artificial Neural Network

The use of Artificial Neural Network (ANN) approaches has gained a significant role over the last decade in the field of predicting the distribution of effects triggered by natural forcing, this being particularly relevant for the development of adequate risk mitigation strategies. Among the most critical features of these approaches, there are the accurate geolocation of the available data as well as their numerosity and spatial distribution. The use of an ANN has never been tested at a national scale in Italy, especially in estimating earthquake-triggered landslides susceptibility. The CEDIT catalogue, the most up-to-date national inventory of earthquake-induced ground effects, was adopted to evaluate the efficiency of an ANN to explain the distribution of landslides over the Italian territory. An ex-post evaluation of the ANN-based susceptibility model was also performed, using a sub-dataset of historical data with lower geolocation precision. The ANN training highly performed in terms of spatial prediction, by partitioning the Italian landscape into slope units. The obtained results returned a distribution of potentially unstable slope units with maximum concentrations primarily distributed in the central Apennines and secondarily in the southern and northern Apennines. Moreover, the Alpine sector clearly appeared to be divided into two areas, a western one with relatively low susceptibility to earthquake-triggered landslides and the eastern sector with higher susceptibility. Our work clearly demonstrates that if funds for risk mitigation were allocated only on the basis of rainfall-induced landslide distribution, large areas highly susceptible to earthquake-triggered landslides would be completely ignored by mitigation plans.</p

Hydrometallurgical recycling of EV lithium-ion batteries: Effects of incineration on the leaching efficiency of metals using sulfuric acid

The growing demand for lithium-ion batteries will result in an increasing flow of spent batteries, which must be recycled to prevent environmental and health problems, while helping to mitigate the raw materials dependence and risks of shortage and promoting a circular economy. Combining pyrometallurgical and hydrometallurgical recycling approaches has been the focus of recent studies, since it can bring many advantages. In this work, the effects of incineration on the leaching efficiency of metals from EV LIBs were evaluated. The thermal process was applied as a pre-treatment for the electrode material, aiming for carbothermic reduction of the valuable metals by the graphite contained in the waste. Leaching efficiencies above 70% were obtained for Li, Mn, Ni and Co after 60 min of leaching even when using 0.5 M sulfuric acid, which can be linked to the formation of more easily leachable compounds during the incineration process. When the incineration temperature was increased (600–700 \ub0C), the intensity of graphite signals decreased and other oxides were identified, possibly due to the increase in oxidative conditions. Higher leaching efficiencies of Mn, Ni, Co, and Li were reached at lower temperatures of incineration (400–500 \ub0C) and at higher leaching times, which could be related to the partial carbothermic reduction of the metals

Recovery of critical metals from EV batteries via thermal treatment and leaching with sulphuric acid at ambient temperature

In the upcoming years, toda\ufds e-mobility will challenge the capacity of sustainable recycling. Due to the presence of organic components (electrolyte, separator, casings, etc.), future recycling technologies will combine thermal pre-treatment followed by hydrometallurgical processing. Despite the ongoing application of such treatment, there is still a lack of information on how applied parameters affect subsequent metal recovery. In this study, both oxidative and reductive conditions in dependence on temperature and time were studied. Qualitative and quantitative characterizations of the samples after treatment were performed followed by leaching with 2 M sulphuric acid at ambient temperature to determine the leachability of valuable metals such as Co, Mn, Ni and Li. Moreover, the negative or positive effect of treatment on the leachability of the main impurities (Cu and Al) was determined. Since the presence of carbon affects the degree of active material reduction, it\u27s content after each thermal treatment was determined as well. If all variables, temperature and time of thermal processing are taken into account, pyrolysis at 700 \ub0C for 30 min is the optimal treatment. Under these conditions, full recovery is reached after 2 min for Li, 5 min for Mn and 10 min for both Co and Ni. In the case of the incineration, only processing at 400 and 500 \ub0C promoted higher recovery of metals, while the treatment at 600 and 700 \ub0C led to the formation of less leachable species

Comparison of the effects of incineration, vacuum pyrolysis and dynamic pyrolysis on the composition of NMC-lithium battery cathode-material production scraps and separation of the current collector

The rising demand for lithium batteries is challenging battery producers to increase their production. This is causing an accumulation of production scrap which must be treated to allow re-utilization of cathode material in production. Several industrial lithium battery recycling processes use thermal pre-treatment in an oxidative or inert atmosphere, or in a vacuum, to separate the battery components and remove organic material. However, a comparison of the effects of incineration, dynamic pyrolysis (under a constant flow of inert gas), and pyrolysis under vacuum on the microstructure and composition of scrap cathode material has not been explored. Scrap cathodes, with active material based on Li(NixMnyCoz)Oj, were subjected to incineration, dynamic pyrolysis, and pyrolysis under vacuum at 450˚, 550˚, and 650\ub0C for 30, 60, 90, and 150 min to determine the best approach to cathode material recovery. While the incineration did not cause any chemical transformation of cathode material, under pyrolysis conditions the organic components in the cathodes triggered carbothermic reduction of the active material, yielding Co3O4, NiO, Mn3O4, and Li2CO3 as products. In the gas by-products, formed from the decomposition of the organic material, CO, CO2, and HF were determined. The decomposition especially of the binder in polyvinylidene fluoride (PVDF) facilitated the separation of the active material from the current collector by mechanical treatment. By subsequent ball milling, the best technique to recover cathode material is the incineration at a temperature higher than 550˚ C and below 650˚ C for at least 90 min, with &gt;95% of recovered active material