Mechanism of Li2S formation and dissolution in Lithium-Sulphur batteries

Insufficient understanding of the mechanism that reversibly converts sulphur into lithium sulphide (Li2S) via soluble polysulphides (PS) hampers the realization of high performance lithium-sulphur cells. Typically Li2S formation is explained by direct electroreduction of a PS to Li2S; however, this is not consistent with the size of the insulating Li2S deposits. Here, we use in situ small and wide angle X-ray scattering (SAXS/WAXS) to track the growth and dissolution of crystalline and amorphous deposits from atomic to sub-micron scales during charge and discharge. Stochastic modelling based on the SAXS data allows quantification of the chemical phase evolution during discharge and charge. We show that Li2S deposits predominantly via disproportionation of transient, solid Li2S2 to form primary Li2S crystallites and solid Li2S4 particles. We further demonstrate that this process happens in reverse during charge. These findings show that the discharge capacity and rate capability in Li-S battery cathodes are therefore limited by mass transport through the increasingly tortuous network of Li2S / Li2S4 / carbon pores rather than electron transport through a passivating surface film

High frequency response of adenine-derived carbon in aqueous electrochemical capacitor

Electrochemical capacitors are attractive power sources, especially when they are able to operate at high frequency (high current regime). In order to meet this requirement their constituents should be made of high conductivity materials with a suitable porosity. In this study, enhanced power and simultaneously high capacitance (120 F g−1 at 1 Hz or 10 A g−1) electrode material obtained from carbonized adenine precursor is presented. A micro/mesoporous character of the carbon with optimal pore size ratio and high surface area was proven by the physicochemical characterization. The beneficial pore structure and morphology resembling highly conductive carbon black, together with a significant nitrogen content (5.5%) allow for high frequency response of aqueous capacitor to be obtained. The carbon/carbon symmetric capacitor (in 1 mol L−1 Li2SO4) has been tested to the voltage of 1.5 V. The cyclic voltammetry indicates a good electrochemical response even at high scan rate (50 mV s−1). The cyclability of the capacitor is comparable to the one operating with commercial carbon (YP50F). The adenine-based capacitor is especially favourable for stationary applications requiring high power.Partners acknowledge M-ERA.NET network, MCIN/AEI/10.13039/501100011033 (Ref. PCI2019–103637), CIBER-BBN, ICTS ‘‘NANBIOSIS’’, ICTS ELECMI node "Laboratorio de Microscopias Avanzadas", National Science Centre, Poland (2018/30/Z/ST4/00901), and Ministrstvo za izobraževanje, znanost in šport for financial support and the grant of Ministry of Science and Higher Education in Poland, no. 0911/SBAD/2101. A.V., B.T., E.T. and R.D. additionally acknowledge financial support from the Slovenian Research Agency (ARRS) research core funding P2–0393.Peer reviewe

Concept and electrochemical mechanism of an Al metal anode - organic cathode battery

Aluminum (Al) batteries are fundamentally a promising future post-Li battery technology. The recently demonstrated concept of an Al-graphite battery represents some significant progress for the technology, but the cell energy density is still very modest and limited by the quantity of the AlCl3 based electrolyte, as it relies on AlCl4- intercalation. For further progress, cathode materials capable of an electrochemical reaction with Al positively charged species are needed. Here such a concept of an Al metal anode - organic cathode battery based on anthraquinone (AQ) electrochemistry with a discharge voltage of 1.1 V is demonstrated. Further improvement of both the cell capacity retention and rate capability is achieved by nano-structured and polymerized cathodes. The intricate electrochemical mechanism is proven to be that the anthraquinone groups undergo reduction of their carbonyl bonds during discharge and become coordinated by AlCl2+ species. Altogether the Al metal anode - AQ cathode cell has almost the double energy density of the state-of-the-art Al-graphite battery

Preparation, characterization and environmental/electrochemical energy storage testing of low-cost biochar from natural chitin obtained via pyrolysis at mild conditions

Chitin (a biopolymer obtained from shellfish industry) was used as precursor for the production of biochars obtained via pyrolysis treatments performed at mild conditions (in the 290–540 °C range). Biochars were physicochemical characterized in order to evaluate the pyrolysis-induced effects in terms of both functional groups and material structure. Moreover, such carbonaceous materials were tested as adsorbent substrates for the removal of target molecules from aqueous environment as well as in solid-gas experiments, to measure the adsorption capacities and selectivity toward CO2. Lastly, biochars were also investigated as possible cathode materials in sustainable and low-cost electrochemical energy storage devices, such as lithium-sulphur (Li-S) batteries. Interestingly, experimental results evidenced that such chitin-derived biochars obtained via pyrolysis at mild conditions are sustainable, low-cost and easy scalable alternative materials suitable for both environmental and energetic applications

New non-graphitizable carbon/nanocrystals hybrids with enhanced electrochemical properties for Na-ion batteries

Resumen del trabajo presentado a la XXXVIII Reunión Bienal de la Real Sociedad Española de Química, celebrada en el Palacio de Congresos de Granada, del 27 de junio al 30 de junio de 2022.Peer reviewe

Linear and Cross-Linked Ionic Liquid Polymers as Binders in Lithium–Sulfur Batteries

A collection of different polymeric ionic liquids (PILs) were explored as cathode binders in lithium–sulfur batteries. The PIL molecular structure, polymer backbone, and polymer architecture were found to influence the cell capacity, the cyclability, and the morphology of the cathode itself. PILs with styrene backbones performed better than the vinyl-based polymer, while cross-linked PILs imparted further improved capacities, cyclability, and reduced overpotentials. Unlike polyvinylidene fluoride, PIL binders mixed with the sulfide species, resulting in more uniformly distributed sulfides in the cathode and better sulfide transport. These features helped to mitigate volume change-induced degradation that typically plagues Li–S batteries. The uptake of polysulfides by PILs also constrains the polysulfide shuttle during battery cycling, leading to better cycling stability. While traditionally binders are viewed only as a “glue” to hold the active material together, PIL binders have additional functions and play an active role during Li–S battery working operation

Synthesis, characterization, and application in rechargeable batteries of CuXS-rGO aerogels

Resumen del trabajo presentado a la XXXVIII Reunión Bienal de la Real Sociedad Española de Química, celebrada en el Palacio de Congresos de Granada, del 27 de junio al 30 de junio de 2022.Authors acknowledge the M-ERA.NET (NOEL) project, PCI2019-103637 funded by MCIN/AEI/10.13039/501100011033.Peer reviewe

Cover Feature: Magnesium Polysulfides: Synthesis, Disproportionation, and Impedance Response in Symmetrical Carbon Electrode Cells (ChemElectroChem 6/2021)

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