A Layered Bi2 Te3 @PPy Cathode for Aqueous Zinc-Ion Batteries: Mechanism and Application in Printed Flexible Batteries.

Low-cost, safe, and environmental-friendly rechargeable aqueous zinc-ion batteries (ZIBs) are promising as next-generation energy storage devices for wearable electronics among other applications. However, sluggish ionic transport kinetics and the unstable electrode structure during ionic insertion/extraction hamper their deployment. Herein, a new cathode material based on a layered metal chalcogenide (LMC), bismuth telluride (Bi2 Te3 ), coated with polypyrrole (PPy) is proposed. Taking advantage of the PPy coating, the Bi2 Te3 @PPy composite presents strong ionic absorption affinity, high oxidation resistance, and high structural stability. The ZIBs based on Bi2 Te3 @PPy cathodes exhibit high capacities and ultra-long lifespans of over 5000 cycles. They also present outstanding stability even under bending. In addition, here the reaction mechanism is analyzed using in situ X-ray diffraction, X-ray photoelectron spectroscopy, and computational tools and it is demonstrated that, in the aqueous system, Zn2+ is not inserted into the cathode as previously assumed. In contrast, proton charge storage dominates the process. Overall, this work not only shows the great potential of LMCs as ZIB cathode materials and the advantages of PPy coating, but also clarifies the charge/discharge mechanism in rechargeable ZIBs based on LMCs.

Nanostructured Li2S Cathodes for Silicon-Sulfur Batteries.

Lithium-sulfur batteries are regarded as an advantageous option for meeting the growing demand for high-energy-density storage, but their commercialization relies on solving the current limitations of both sulfur cathodes and lithium metal anodes. In this scenario, the implementation of lithium sulfide (Li2S) cathodes compatible with alternative anode materials such as silicon has the potential to alleviate the safety concerns associated with lithium metal. In this direction, here, we report a sulfur cathode based on Li2S nanocrystals grown on a catalytic host consisting of CoFeP nanoparticles supported on tubular carbon nitride. Nanosized Li2S is incorporated into the host by a scalable liquid infiltration-evaporation method. Theoretical calculations and experimental results demonstrate that the CoFeP-CN composite can boost the polysulfide adsorption/conversion reaction kinetics and strongly reduce the initial overpotential activation barrier by stretching the Li-S bonds of Li2S. Besides, the ultrasmall size of the Li2S particles in the Li2S-CoFeP-CN composite cathode facilitates the initial activation. Overall, the Li2S-CoFeP-CN electrodes exhibit a low activation barrier of 2.56 V, a high initial capacity of 991 mA h gLi2S-1, and outstanding cyclability with a small fading rate of 0.029% per cycle over 800 cycles. Moreover, Si/Li2S full cells are assembled using the nanostructured Li2S-CoFeP-CN cathode and a prelithiated anode based on graphite-supported silicon nanowires. These Si/Li2S cells demonstrate high initial discharge capacities above 900 mA h gLi2S-1 and good cyclability with a capacity fading rate of 0.28% per cycle over 150 cycles.

A 3d-4d-5d High Entropy Alloy as a Bifunctional Oxygen Catalyst for Robust Aqueous Zinc-Air Batteries.

High entropy alloys (HEAs) are highly suitable candidate catalysts for oxygen evolution and reduction reactions (OER/ORR) as they offer numerous parameters for optimizing the electronic structure and catalytic sites. Herein, FeCoNiMoW HEA nanoparticles are synthesized using a solution-based low-temperature approach. Such FeCoNiMoW nanoparticles show high entropy properties, subtle lattice distortions, and modulated electronic structure, leading to superior OER performance with an overpotential of 233 mV at 10 mA cm-2 and 276 mV at 100 mA cm-2 . Density functional theory calculations reveal the electronic structures of the FeCoNiMoW active sites with an optimized d-band center position that enables suitable adsorption of OOH* intermediates and reduces the Gibbs free energy barrier in the OER process. Aqueous zinc-air batteries (ZABs) based on this HEA demonstrate a high open circuit potential of 1.59 V, a peak power density of 116.9 mW cm-2 , a specific capacity of 857 mAh gZn -1 , and excellent stability for over 660 h of continuous charge-discharge cycles. Flexible and solid ZABs are also assembled and tested, displaying excellent charge-discharge performance at different bending angles. This work shows the significance of 4d/5d metal-modulated electronic structure and optimized adsorption ability to improve the performance of OER/ORR, ZABs, and beyond.

Bottom-Up Synthesis of SnTe-Based Thermoelectric Composites.

There is a need for the development of lead-free thermoelectric materials for medium-/high-temperature applications. Here, we report a thiol-free tin telluride (SnTe) precursor that can be thermally decomposed to produce SnTe crystals with sizes ranging from tens to several hundreds of nanometers. We further engineer SnTe-Cu2SnTe3 nanocomposites with a homogeneous phase distribution by decomposing the liquid SnTe precursor containing a dispersion of Cu1.5Te colloidal nanoparticles. The presence of Cu within the SnTe and the segregated semimetallic Cu2SnTe3 phase effectively improves the electrical conductivity of SnTe while simultaneously reducing the lattice thermal conductivity without compromising the Seebeck coefficient. Overall, power factors up to 3.63 mW m-1 K-2 and thermoelectric figures of merit up to 1.04 are obtained at 823 K, which represent a 167% enhancement compared with pristine SnTe.

CoFeNiMnZnB as a High-Entropy Metal Boride to Boost the Oxygen Evolution Reaction.

High-entropy materials offer numerous advantages as catalysts, including a flexible composition to tune the catalytic activity and selectivity and a large variety of adsorption/reaction sites for multistep or multiple reactions. Herein, we report on the synthesis, properties, and electrocatalytic performance of an amorphous high-entropy boride based on abundant transition metals, CoFeNiMnZnB. This metal boride provides excellent performance toward the oxygen evolution reaction (OER), including a low overpotential of 261 mV at 10 mA cm-2, a reduced Tafel slope of 56.8 mV dec-1, and very high stability. The outstanding OER performance of CoFeNiMnZnB is attributed to the synergistic interactions between the different metals, the leaching of Zn ions, the generation of oxygen vacancies, and the in situ formation of an amorphous oxyhydroxide at the CoFeNiMnZnB surface during the OER.