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Deep eutectic solvents (DESs) have garnered attention in Li-ion battery (LIB) recycling due to their declared eco-friendly attributes and adjustable metal dissolution selectivity, offering a promising avenue for recycling processes. However, DESs currently lack competitiveness compared to mineral acids, commonly used in industrial-scale LIB recycling. Current research primarily focuses on optimizing DES formulation and experimental conditions to maximize metal dissolution yields in standalone leaching experiments. While achieving yields comparable to traditional leaching systems is important, extensive DES reuse is vital for overall recycling feasibility. To achieve this, evaluating the metal dissolution mechanism can assist in estimating DES consumption rates and assessing process makeup stream costs. The selection of appropriate metal recovery and DES regeneration strategies is essential to enable subsequent reuse over multiple cycles. Finally, decomposition of DES components should be avoided throughout the designed recycling process, as by-products can impact leaching efficiency and compromise the safety and environmental friendliness of DES. In this review, these aspects are emphasized with the aim of directing research efforts away from simply pursuing the maximization of metal dissolution efficiency, towards a broader view focusing on the application of DES beyond the laboratory scale., (© 2024 Wiley-VCH GmbH.)

The application of deep eutectic solvents (DESs) to dissolve metal oxides in lithium-ion batteries (LIBs) recycling represents a green technological alternative to the mineral acids employed in hydrometallurgical recycling processes. However, DESs are much more expensive than mineral acids and must be reused to ensure economic feasibility of LIB recycling. To evaluate DES reusability, the role of the choline chloride-ethylene glycol DES decomposition products on metal oxides dissolution was investigated. The temperatures generally applied to carry on this DES leaching induced the formation of decomposition products that ultimately improved the ability to dissolve LIB metal oxides. The characterization of DES decomposition products revealed that the improved metal dissolution was mainly determined by the formation of Cl 3 - , which was proposed to play a pivotal role in the oxidative dissolution of LIB metal oxides., (© 2022 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

p-Cu 2 O/n-TiO 2 photoanodes were produced by electrodeposition of octahedral p-type Cu 2 O nanoparticles over n-type TiO 2 nanotubes. The photoresponse of the composite p-n photoanodes was evaluated in photoelectrochemical cells operating at "zero-bias" conditions under either visible or UV-vis irradiation. In both operating conditions, the produced electrodes invariably followed the p-n-based photoanode operations but exhibited lower photoelectrochemical performance as compared to the bare n-TiO 2 photoanode under UV-vis light. The reported experimental analysis evidenced that such decreased photoactivity is mainly induced by the scarce efficiency of the nanosized p-n interfaces upon irradiation. To overcome such limitation, a restructuring of the originally electrodeposited p-Cu 2 O was promoted, following a photoelectrochemical post-treatment strategy. p-Cu 2 O, restructured in a 2D leaf-like morphology, allowed reaching an improved photoelectrochemical performance for the p-n-based photoanode under UV-vis light. As compared to the bare n-TiO 2 behavior, such improvement consisted of photoanodic currents up to three times larger. An analysis of the mechanisms driving the transition from compact (∼100 nm) octahedral p-Cu 2 O to wider (∼1 μm) 2D leaf-like structures was performed, which highlighted the pivotal role played by the irradiated n-TiO 2 NTs.

The direct synthesis of high-value products from end-of-life Li-ion batteries (LIBs), avoiding the complex and costly separation of the different elements, can be reached through a competitive recycling strategy. Here, we propose the simultaneous synthesis of reduced graphene oxide (rGO) and lithium-manganese-rich (Li 1.2 Mn 0.55 Ni 0.15 Co 0.1 O 2 - LMR) cathode material from end-of-life LIBs. The electrode powder recovered after LIBs mechanical pretreatment was directly subjected to the Hummers' method. This way, quantitative extraction of the target metals (Co, Ni, Mn) and oxidation of graphite to graphene oxide (GO) were simultaneously achieved, and a Mn-rich metal solution resulted after GO filtration, owing to the use of KMnO 4 as an oxidizing agent. This solution, which would routinely constitute a heavy-metal liquid waste, was directly employed for the synthesis of Li 1.2 Mn 0.55 Ni 0.15 Co 0.1 O 2 cathode material. XPS measurements demonstrate the presence in the synthesized LMR of Cu 2+ , SO 4 2- , and SiO 4 4- impurities, which were previously proposed as effective doping species and can thus explain the improved electrochemical performance of recovered LMR. The GO recovered by filtration was reduced to rGO by using ascorbic acid. To evaluate the role of graphite lithiation/delithiation during battery cycling on rGO production, the implemented synthesis procedure was replicated starting from commercial graphite and from the graphite recovered by a consolidated acidic-reductive leaching procedure for metals extraction. Raman and XPS analysis disclosed that cyclic lithiation/delithiation of graphite during battery life cycle facilitates the graphite exfoliation and thus significantly increases conversion to rGO., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

The increase in the annual flux of the end-of-life photovoltaic panels (EoL-PVPs) imposed the development of effective recycling strategies to reach EU regulation targets (i.e. 80% recycling; 85% recovery, starting from August 2018). The recycling targets in a PVP are generally glass, photovoltaic cell and metals, while no scientific paper or patent addressed polymeric fractions recycling and recovery, i.e. encapsulant polymer (EVA) and backsheet (Tedlar), starting from preliminarily milled EoL-PVPs. In the present study an optimization following the solvent treatment operation of the basic Photolife process (demonstrated at pilot scale), was proposed (lab scale) and validated (micropilot scale), focusing on polymers separation and metals recovery. The optimization was performed by testing 4 different processes. Specifically, the selectivity of the filtration operation (subsequent the solvent treatment) on polymers separation grade was evaluated, demonstrating that Tedlar can be effectively separated from EVA residues. Moreover, in comparison to the basic Photolife, a further operation was introduced treating thermally the EVA residues (containing the PV cell). The metal extraction yields highlighted the effectiveness of that strategy in comparison with direct extraction from the uncombusted EVA residues. Processing 100 Kg of crushed material, 0.03 Kg of Ag, 45.5 Kg of high value glass, 10 Kg of Al scraps and 1.2 Kg of metallic filaments can be recovered. Thanks to the optimization the recycling rate of the implemented process grew up to 82% (75% during demonstration of the basic Photolife process), while the recovery was estimated at 94%. Remarkably, these rates get over with EU Directive., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: the present work was developed within the activities of the ORIFO project, co-funded by the Italian Ministry of the Environment and Sea Protection, which was developed as optimization of the end-of-life photovoltaic panels recycling process developed in the previous European project PHOTOLIFE (LIFE13 ENV/IT/001033), co-funded by EU LIFE+ program., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Noncovalent DNA functionalization is one of the most used routes for the easy dispersion of carbon nanotubes (CNTs) yielding DNA-CNTs complexes with promising applications. Definition of the structure of adsorbed DNA is crucial, but the organization of polymer at the carbon interface is far from being understood. In comparison to single-walled nanotubes, not much effort has been devoted to assessing the structure of the adsorbed DNA on multiwalled carbon nanotubes (MWCNTs), where their metallic nature, large size, and polydispersity represent serious obstacles for both experimental and theoretical studies. As a contribution to fill this lack in these aspects, we investigated DNA-MWCNT complexes by dielectric spectroscopy (DS) which is sensitive to even small changes in the charge distribution at charged interfaces and was largely employed in studying the electric and conformational properties of polyelectrolytes, such as DNA, in aqueous solutions and at interfaces. The dielectric relaxation in the MHz range is the signature of DNA adsorption on CNTs and sheds light on its conformational properties. A detailed analysis of the conductivity of the DNA-MWCNT suspensions unequivocally proves that DNA is adsorbed in a single-stranded conformation while excess DNA reassociates without interfering with the stability of the complexes.