A Radical Pathway and Stabilized Li Anode Enabled by Halide Quaternary Ammonium Electrolyte Additives for Lithium-Sulfur Batteries.

Passivation of the sulfur cathode by insulating lithium sulfide restricts the reversibility and sulfur utilization of Li-S batteries. 3D nucleation of Li2 S enabled by radical conversion may significantly boost the redox kinetics. Electrolytes with high donor number (DN) solvents allow for tri-sulfur (S3 ⋅- ) radicals as intermediates, however, the catastrophic reactivity of such solvents with Li anodes pose a great challenge for their practical application. Here, we propose the use of quaternary ammonium salts as electrolyte additives, which can preserve the partial high-DN characteristics that trigger the S3 ⋅- radical pathway, and inhibit the growth of Li dendrites. Li-S batteries with tetrapropylammonium bromide (T3Br) electrolyte additive deliver the outstanding cycling stability (700 cycles at 1 C with a low-capacity decay rate of 0.049 % per cycle), and high capacity under a lean electrolyte of 5 µLelectrolyte mgsulfur -1 . This work opens a new avenue for the development of electrolyte additives for Li-S batteries.

An Adaptive Multispectral Mechano-Optical System for Multipurpose Applications.

Mechano-optical systems with on-demand adaptability and a broad spectrum from the visible to microwave are critical for complex multiband electromagnetic (EM) applications. Most existing material systems merely have dynamic optical or microwave tunability because their EM wave response is strongly wavelength-dependent. Inspired by cephalopod skin, we develop an adaptive multispectral mechano-optical system based on bilayer acrylic dielectric elastomer (ADE)/silver nanowire (AgNW) films, which reconfigures the surface morphology between wrinkles and cracks via mechanical contraction and stretching. Such morphological evolution regulates the direct transmission/reflection and scattering behavior of visible-infrared light and simultaneously alters the conductive network in a AgNW film to influence its microwave characteristics. The designed system features switching between visible-infrared-microwave transparency and opacity, continuous regulation, wide spectral window (0.38-15.5 µm and 24,200-36,600 µm), excellent recyclability (500 times), and rapid response time (<1 s). These grant the system great potential as platforms for various promising applications such as smart windows, switchable EM devices, dynamic thermal management, adaptive visual stealth, and human motion detection.

Multi-Domain versus Single-Domain: A Magnetic Field is Not a Must for Promoting Spin-Polarized Water Oxidation.

The reaction kinetics of spin-polarized oxygen evolution reaction (OER) can be enhanced by ferromagnetic (FM) catalysts under an external magnetic field. However, applying a magnetic field necessitates additional energy consumption and creates design difficulties for OER. Herein, we demonstrate that a single-domain FM catalyst without external magnetic fields exhibits a similar OER increment to its magnetized multi-domain one. The evidence is given by comparing the pH-dependent increment of OER on multi- and single-domain FM catalysts with or without a magnetic field. The intrinsic activity of a single-domain catalyst is higher than that of a multi-domain counterpart. The latter can be promoted to approach the former by the magnetization effect. Reducing the FM catalyst size into the single-domain region, the spin-polarized OER performance can be achieved without a magnetic field, illustrating an external magnetic field is not a requirement to reap the benefits of magnetic catalysts.

A Lightweight, Elastic, and Thermally Insulating Stealth Foam With High Infrared-Radar Compatibility.

The development of infrared-radar compatible materials/devices is challenging because the requirements of material properties between infrared and radar stealth are contradictory. Herein, a composite of poly(3, 4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) coated melamine foam is designed to integrate the advantages of the dual materials and the created heterogeneous interface between them. The as-designed PEDOT:PSS@melamine composite shows excellent mechanical properties, outstanding thermal insulation, and improved thermal infrared stealth performance. The relevant superb radar stealth performance including the minimum reflection loss value of -57.57 dB, the optimum ultra-wide bandwidth of 10.52 GHz, and the simulation of radar cross section reduction value of 17.68 dB m2 , can be achieved. The optimal specific electromagnetic wave absorption performance can reach up as high as 3263.02 dB·cm3 g-1 . The average electromagnetic interference shielding effectiveness value can be 30.80 dB. This study provides an approach for the design of high-performance stealth materials with infrared-radar compatibility.

Ferromagnetic-Antiferromagnetic Coupling Core-Shell Nanoparticles with Spin Conservation for Water Oxidation.

Rational design of active oxygen evolution reaction (OER) catalysts is critical for the overall efficiency of water electrolysis. The differing spin states of the OER reactants and products is one of the factors that slows OER kinetics. Thus, spin conservation plays a crucial role in enhancing OER performance. In this work, ferromagnetic (FM)-antiferromagnetic (AFM) Fe3 O4 @Ni(OH)2 core-shell catalysts are designed. The interfacial FM-AFM coupling of these catalysts facilitates selective removal of electrons with spin direction opposing the magnetic moment of FM core, improving OER kinetics. The shell thickness is found critical in retaining the coupling effect for OER enhancement. The magnetic domain structure of the FM core also plays a critical role. With a multiple domain core, the applied magnetic field aligns the magnetic domains, optimizing the electron transport process. A significant enhancement of OER activity is observed for the multiple domain core catalysts. With a single-domain FM core with ordered magnetic dipoles, the spin-selective electron transport with minimal scattering is facilitated even without an applied magnetic field. A magnetism/OER activity model therefore hypothesizes that depends on two main parameters: interfacial spin coupling and domain structure. These findings provide new design principles for active OER catalysts.

SmCo5 with a Reconstructed Oxyhydroxide Surface for Spin-Selective Water Oxidation at Elevated Temperature.

The efficiency of electrolytic hydrogen production is limited by the slow reaction kinetics of oxygen evolution reaction (OER). Surface-reconstructed ferromagnetic (FM) catalysts with a spin-pinning effect at the FM/oxyhydroxide interface could enhance the spin-dependent OER kinetics. However, in real-life applications, electrolyzers are operated at elevated temperature, which may disrupt the spin orientations of FM catalysts and limit their performance. In this study, we prepared surface-reconstructed SmCo5 /CoOx Hy , which possesses polarized spins at the FM/oxyhydroxide interface that lead to excellent OER activity. These interfacial polarized spins could be further aligned through a magnetization process, which further enhanced the OER performance. Moreover, the operation temperature was elevated to mimic the practical operation conditions of water electrolyzers. It was found that the OER activity enhancement of the magnetized SmCo5 /CoOx Hy catalyst could be preserved up to 60 °C.

Anodic Oxidation Enabled Cation Leaching for Promoting Surface Reconstruction in Water Oxidation.

A rational design for oxygen evolution reaction (OER) catalysts is pivotal to the overall efficiency of water electrolysis. Much work has been devoted to understanding cation leaching and surface reconstruction of very active electrocatalysts, but little on intentionally promoting the surface in a controlled fashion. We now report controllable anodic leaching of Cr in CoCr2 O4 by activating the pristine material at high potential, which enables the transformation of inactive spinel CoCr2 O4 into a highly active catalyst. The depletion of Cr and consumption of lattice oxygen facilitate surface defects and oxygen vacancies, exposing Co species to reconstruct into active Co oxyhydroxides differ from CoOOH. A novel mechanism with the evolution of tetrahedrally coordinated surface cation into octahedral configuration via non-concerted proton-electron transfer is proposed. This work shows the importance of controlled anodic potential in modifying the surface chemistry of electrocatalysts.

Enhancing the Charge Transportation Ability of Yolk-Shell Structure for High-Rate Sodium and Potassium Storage.

The microstructure of large-capacity anodes is of great importance in determining the performance of sodium- and potassium-ion batteries. Yolk-shell nanostructures promise excellent structural stability but suffer from insufficient charge transfer rate during cycles. Herein, we tackle this challenge by constructing a single-walled carbon nanotube (SWNT) internally bridged yolk-shell structure, inside which SWNTs cover the surface of the yolk and connect the yolk and shell, for better electron/ion transportation. Combining the merits of both yolk-shell structure and conductive SWNT channels, the as-prepared Fe1-xS/SWNT@C composite manifests high reversible capacity and ultralong cycling stability up to 8700 cycles. Moreover, it displays the best rate capability (317 mA h g-1 at 20 A g-1 for Na+ and 236 mA h g-1 at 10 A g-1 for K+) among the reported yolk-shell structures and iron-sulfide-based anodes thus far. The kinetic analysis and density functional theory calculations further reveal that the Fe1-xS/SWNT heterointerface can effectively enhance the reversibility of K+ storage and decrease the K+ diffusion energy barrier, leading to excellent pseudocapacitive behavior and fast ion transportation for outstanding rate capability.

Antiferromagnetic Inverse Spinel Oxide LiCoVO4 with Spin-Polarized Channels for Water Oxidation.

Exploring highly efficient catalysts for the oxygen evolution reaction (OER) is essential for water electrolysis. Cost-effective transition-metal oxides with reasonable activity are raising attention. Recently, OER reactants' and products' differing spin configurations have been thought to cause slow reaction kinetics. Catalysts with magnetically polarized channels could selectively remove electrons with opposite magnetic moment and conserve overall spin during OER, enhancing triplet state oxygen molecule evolution. Herein, antiferromagnetic inverse spinel oxide LiCoVO4 is found to contain d7 Co2+ ions that can be stabilized under active octahedral sites, possessing high spin states S = 3/2 (t2g 5 eg 2 ). With high spin configuration, each Co2+ ion has an ideal magnetic moment of 3 µB , allowing the edge-shared Co2+ octahedra in spinel to be magnetically polarized. Density functional theory simulation results show that the layered antiferromagnetic LiCoVO4 studied contains magnetically polarized channels. The average magnetic moment (µave ) per transition-metal atom in the spin conduction channel is around 2.66 µB . Such channels are able to enhance the selective removal of spin-oriented electrons from the reactants during the OER, which facilitates the accumulation of appropriate magnetic moments for triplet oxygen molecule evolution. In addition, the LiCoVO4 reported has been identified as an oxide catalyst with excellent OER activity.

Mastering Surface Reconstruction of Metastable Spinel Oxides for Better Water Oxidation.

Developing highly active electrocatalysts for oxygen evolution reaction (OER) is critical for the effectiveness of water splitting. Low-cost spinel oxides have attracted increasing interest as alternatives to noble metal-based OER catalysts. A rational design of spinel catalysts can be guided by studying the structural/elemental properties that determine the reaction mechanism and activity. Here, using density functional theory (DFT) calculations, it is found that the relative position of O p-band and MOh (Co and Ni in octahedron) d-band center in ZnCo2- x Nix O4 (x = 0-2) correlates with its stability as well as the possibility for lattice oxygen to participate in OER. Therefore, it is testified by synthesizing ZnCo2- x Nix O4 spinel oxides, investigating their OER performance and surface evolution. Stable ZnCo2- x Nix O4 (x = 0-0.4) follows adsorbate evolving mechanism under OER conditions. Lattice oxygen participates in the OER of metastable ZnCo2- x Nix O4 (x = 0.6, 0.8) which gives rise to continuously formed oxyhydroxide as surface-active species and consequently enhances activity. ZnCo1.2 Ni0.8 O4 exhibits performance superior to the benchmarked IrO2 . This work illuminates the design of highly active metastable spinel electrocatalysts through the prediction of the reaction mechanism and OER activity by determining the relative positions of the O p-band and the MOh d-band center.

Equilibrium and Dynamic Absorption of Electrolyte Species in Cation/Anion Exchange Membranes of Vanadium Redox Flow Batteries.

Vanadium redox flow batteries (VRFBs) rely on ion exchange membranes (IEMs) to separate the positive and negative compartments while maintaining electrical neutrality of the cell, by allowing the transport of ionic charge carriers. Cation exchange membranes (CEMs) and anion exchange membranes (AEMs), the two principal types of IEM, have both been employed in VRFBs. The performance of these IEMs can be influenced by the absorption of species from the electrolyte. In this study, a typical commercial CEM (Nafion 117) and AEM (FAP 450), were examined with respect to vanadium uptake, after exposure to electrolyte at different states of charge. The two types of membrane were found to behave very differently, with the AEM showing very high selectivity for VV , which resulted in a significant increase in area-specific resistivity. In contrast, the CEM absorbed VII more strongly than vanadium in other oxidation states. These findings are essential for the development of an effective membrane for VRFB applications.