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Considering the worldwide market of batteries and supercapacitors, the (partial or total) replacement of conventional fossil-derived carbonates with bio-based ones in electrolyte formulations would allow the production of safer and more sustainable devices. In this work, embracing the 7 th principle of green chemistry, glycerol derivatives (namely glycerol carbonate and solketal carbonate) are tested as solvents and additives for electrolyte formulations. Glycerol carbonate is innovatively employed as promising electrolyte solvent for electric double-layer capacitors with excellent performances. On the other hand, a solketal carbonate-laden liquid electrolyte is investigated for potassium-based batteries, showing a rather stable electrochemical behaviour and performance close to those of commercial oil-derived alternatives., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Potassium batteries show interesting peculiarities as large-scale energy storage systems and, in this scenario, the formulation of polymer electrolytes obtained from sustainable resources or waste-derived products represents a milestone activity. In this study, a lignin-based membrane is designed by crosslinking a pre-oxidized Kraft lignin matrix with an ethoxylated difunctional oligomer, leading to self-standing membranes that are able to incorporate solvated potassium salts. The in-depth electrochemical characterization highlights a wide stability window (up to 4 V) and an ionic conductivity exceeding 10 -3  S cm -1 at ambient temperature. When potassium metal cell prototypes are assembled, the lignin-based electrolyte attains significant electrochemical performances, with an initial specific capacity of 168 mAh g -1 at 0.05 A g -1 and an excellent operation for more than 200 cycles, which is an unprecedented outcome for biosourced systems in potassium batteries., (© 2022 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Manufactured globally on industrial scale, cyclodextrins (CD) are cyclic oligosaccharides produced by enzymatic conversion of starch. Their typical structure of truncated cone can host a wide variety of guest molecules to create inclusion complexes; indeed, we daily use CD as unseen components of food, cosmetics, textiles and pharmaceutical excipients. The synthesis of active material composites from CD resources can enable or enlarge the effective utilization of these products in the battery industry with some economical as well as environmental benefits. New and simple strategies are here presented for the synthesis of nanostructured silicon and sulfur composite materials with carbonized hyper cross-linked CD (nanosponges) that show satisfactory performance as high-capacity electrodes. For the sulfur cathode, the mesoporous carbon host limits polysulfide dissolution and shuttle effects and guarantees stable cycling performance. The embedding of silicon nanoparticles into the carbonized nanosponge allows to achieve high capacity and excellent cycling performance. Moreover, due to the high surface area of the silicon composite, the characteristics at the electrode/electrolyte interface dominate the overall electrochemical reversibility, opening a detailed analysis on the behavior of the material in different electrolytes. We show that the use of commercial LP30 electrolyte causes a larger capacity fade, and this is associated with different solid electrolyte interface layer formation and it is also demonstrated that fluoroethylene carbonate addition can significantly increase the capacity retention and the overall performance of our nanostructured Si/C composite in both ether-based and LP30 electrolytes. As a result, an integration of the Si/C and S/C composites is proposed to achieve a complete lithiated Si-S cell., (© 2021 Wiley-VCH GmbH.)

In Li-S batteries, it is important to ensure efficient reversible conversion of sulfur to lithium polysulfide (LiPS). Shuttling effects caused by LiPS dissolution can lead to reduced performance and cycle life. Although carbon materials rely on physical trapping of polysulfides, polar oxide surfaces can chemically bind LiPS to improve the stability of sulfur cathodes. We show a simple synthetic method that allows high sulfur loading into mesoporous carbon preloaded with spatially localized nanoparticles of several Magnéli-phase titanium oxide (Ti n O 2n-1 ). This material simultaneously suppresses polysulfide shuttling phenomena by chemically binding Li polysulfides onto several Magnéli-phase surfaces in a single cathode and ensures physical confinement of sulfur and LiPS. The synergy between chemical immobilization of significant quantities of LiPS at the surface of several Ti n O 2n-1 phases and physical entrapment results in coulombically efficient high-rate cathodes with long cycle life and high capacity. These cathodes function efficiently at low electrolyte-to-sulfur ratios to provide high gravimetric and volumetric capacities in comparison with their highly porous carbon counterparts. Assembled coin cells have an initial discharge capacity of 1100 mAh g -1 at 0.1C and maintain a reversible capacity of 520 mAh g -1 at 0.2C for more than 500 cycles. Even at 1C, the cell loses only 0.06 % per cycle for 1000 cycles with a coulombic efficiency close to 99 %., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Fundamental research on Li-O 2 batteries remains critical, and the nature of the reactions and stability are paramount for realising the promise of the Li-O 2 system. We report that indium tin oxide (ITO) nanocrystals with supported 1-2 nm oxygen evolution reaction (OER) catalyst Ru/RuO x nanoparticles (NPs) demonstrate efficient OER processes, reduce the recharge overpotential of the cell significantly and maintain catalytic activity to promote a consistent cycling discharge potential in Li-O 2 cells even when the ITO support nanocrystals deteriorate from the very first cycle. The Ru/RuO x nanoparticles lower the charge overpotential compared with those for ITO and carbon-only cathodes and have the greatest effect in DMSO electrolytes with a solution-processable F-free carboxymethyl cellulose (CMC) binder (<3.5 V) instead of polyvinylidene fluoride (PVDF). The Ru/RuO x /ITO nanocrystalline materials in DMSO provide efficient Li 2 O 2 decomposition from within the cathode during cycling. We demonstrate that the ITO is actually unstable from the first cycle and is modified by chemical etching, but the Ru/RuO x NPs remain effective OER catalysts for Li 2 O 2 during cycling. The CMC binders avoid PVDF-based side-reactions and improve the cyclability. The deterioration of the ITO nanocrystals is mitigated significantly in cathodes with a CMC binder, and the cells show good cycle life. In mixed DMSO-EMITFSI [EMITFSI=1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide] ionic liquid electrolytes, the Ru/RuO x /ITO materials in Li-O 2 cells cycle very well and maintain a consistently very low charge overpotential of 0.5-0.8 V., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)