Ti-B-O System for Catalyzing Boron Nitride Nanotube Growth.

Chemical vapor deposition (CVD) stands out as the most promising method for cost-effective production of high-quality boron nitride nanotubes (BNNTs). Catalysts play a crucial role in BNNT synthesis. This work delves into the impact of oxygen (O) on Ti-based catalysts during the CVD growth of BNNTs. In contrast to the B/TiB2 nanoparticles (NPs) and B/TiN NPs systems, the oxygen-containing precursor B/TiO2 NPs remarkably catalyzes the growth of high-quality and high-purity BNNTs across a wider range of synthesis parameters. Subsequent analyses reveal that TiBO3 acts as an active catalyst, facilitating BNNT growth in Ti-based catalyst systems. Moreover, the nanocomposite film synthesized from BNNTs and PVDF-HFP exhibits excellent mechanical properties and heat dissipation capabilities. Utilizing the nanocomposite film as a thermal interface material effectively enhances the heat dissipation for a 5 W light-emitting diode (LED) chip. Consequently, our research confirms the effectiveness of the Ti-B-O system in catalyzing BNNT growth.

High-Fluidity/High-Strength Dual-Layer Gel Electrolytes Enable Ultra-Flexible and Dendrite-Free Fiber-Shaped Aqueous Zinc Metal Battery.

Fiber-shaped aqueous zinc-ion batteries (FAZIBs) with intrinsic safety, highcapacity, and superb omnidirectional flexibility hold promise for wearable energy-supply devices. However, the interfacial separation of fiber-shaped electrodes and electrolytes caused by Zinc (Zn) stripping process and severe Zn dendrites occurring at the folded area under bending condition seriously restricts FAZIBs' practical application. Here, an advanced confinement encapsulation strategy is originally reported to construct dual-layer gel electrolyte consisting of high-fluidity polyvinyl alcohol-Zn acetate inner layer and high-strength Zn alginate outer layer for fiber-shaped Zn anode. Benefiting from the synergistic effect of inner-outer gel electrolyte and the formation of solid electrolyte interphase on Zn anode surface by lysine additive, the resulting fiber-shaped Zn-Zn symmetric cell delivers long cycling life over 800 h at 1 mA cm-2 with dynamic bending frequency of 0.1 Hz. The finite element simulation further confirms that dual-layer gel electrolyte can effectively suppress the interfacial separation arising from the Zn stripping and bending process. More importantly, a robust twisted fiber-shaped Zn/zinc hexacyanoferrate battery based on dual-layer gel electrolyte is successfully assembled, achieving a remarkable capacity retention of 97.7% after bending 500 cycles. Therefore, such novel dual-layer gel electrolyte design paves the way for the development of long-life fiber-shaped aqueous metal batteries.

Molecular Engineering Enables Hydrogel Electrolyte with Ionic Hopping Migration and Self-Healability toward Dendrite-Free Zinc-Metal Anodes.

Hydrogel electrolytes (HEs), characterized by intrinsic safety, mechanical stability, and biocompatibility, can promote the development of flexible aqueous zinc-ion batteries (FAZIBs). However, current FAZIB technology is severely restricted by the uncontrollable dendrite growth arising from undesirable reactions between the HEs with sluggish ionic conductivity and Zn metal. To overcome this challenge, this work proposes a molecular engineering strategy, which involves the introduction of oxygen-rich poly(urea-urethane) (OR-PUU) into polyacrylamide (PAM)-based HEs. The OR-PUU/PAM HEs facilitate rapid ion transfer through their ionic hopping migration mechanism, resulting in uniform and orderly Zn2+ deposition. The abundant polar groups on the OR-PUU molecules in OR-PUU/PAM HEs break the inherent H-bond network, tune the solvation structure of hydrated Zn2+, and inhibit the occurrence of side reactions. Moreover, the interaction of hierarchical H-bonds in the OR-PUU/PAM HEs endows them with self-healability, enabling in situ repair of cracks induced by plating/stripping. Consequently, Zn symmetric cells incorporating the novel OR-PUU/PAM HEs exhibit a long cycling life of 2000 h. The resulting Zn-MnO2 battery displays a low capacity decay rate of 0.009% over 2000 cycles at 2000 mA g-1. Overall, this work provides valuable insights to facilitate the realization of dendrite-free Zn-metal anodes through the molecular engineering of HEs.

Efficient Catalysis of Ultrathin Two-Dimensional Fe2 O3 -CoP Heterostructure Nanosheets for Polysulfide Redox Reactions.

The "shuttle effect" and slow redox reactions of Li-S batteries limit their practical application. To solve these problems, a judicious catalyst design for improved battery cycle life and rate performance is essential. Herein, this issue is addressed by modifying the Li-S battery separator using a 2D Fe2 O3 -CoP heterostructure that combines the dual functions of polar Fe2 O3 and high-conductivity CoP. The synthesized ultrathin nanostructure exposes well-dispersed active sites and shortens the ion diffusion paths. Theoretical calculations, electrochemical tests, and in situ Raman spectroscopy measurements reveal that the heterostructure facilitates the inhibition of polysulfide shuttling and enhances the electrode kinetics. A sulfur cathode constructed using the Fe2 O3 -CoP-based separator provides an astonishing capacity of 1346 mAh g-1 at 0.2 C and a high capacity retention of ≈84.5%. Even at a high sulfur loading of 5.42 mg cm-2 , it shows an area capacity of 5.90 mAh cm-2 . This study provides useful insights into the design of new catalytic materials for Li-S batteries.

Construction of Medusa-Like Adhesive Carbon Nanotube Array Induced by Deformation of Alumina Sheets.

To change the binary structure of nanotube and nanotube array in vertically aligned carbon nanotube arrays, this work deposits regularly arranged amorphous alumina sheets on the classical array growth catalyst (10 nm-thick alumina and 2 nm-thick iron) and obtains an array similar to the Medusa head. Subsequent experiments revealed that these alumina sheets show both unstable and stable qualities during growth: unstable in that they thermally deform and change their newly discovered characteristics of blocking carbon source diffusion, which regulates the nanotube growth order in specific areas; stable in that they withstand the deformation caused by heat and sequential growth of nanotubes, serving as a substrate and buffer layer for Medusa's hair, i.e., nanotube bundles on the array surface. Their combination splits this binary structure into a tertiary architecture consisting of nanotubes, nanotube bundles, and the array spanning nano-, micro-, and milli-meter. Benefiting from this structure, this array exhibits a unique near-isotropic adhesion characteristic compared to existing reports and outperforms classical and patterned arrays with the same classical catalyst and growth conditions.

In Situ Etching of Multifunctional Three-Dimensional Interfacial Layers for the Construction of Porous Zn Anodes with Enhanced Surface Textures.

Aqueous Zn-ion batteries offer the advantages of greater security and lower fabrication costs over their lithium-ion counterparts. However, their further advancement and practical application are hindered by the drastic decay in their performance due to the uncontrollable dendrite growth on Zn anodes. In this study, we fabricated a versatile three-dimensional (3D) interfacial layer (3D PVDF-Zn(TFO)2 (PVDF: poly(vinylidene fluoride); TFO: trifluoromethanesulfonate), which simultaneously formed porous Zn-metal anodes (PZn) with an enhanced (002) texture, via a in situ etching scheme. The 3D PVDF-Zn(TFO)2@PZn symmetrical cells leverage the advantages of surface coating and 3D porous architectures to yield extra-long cyclic lifetimes of over 5300 h (0.1 mA cm-2). The fabricated anodes were found to be compatible with MnO2 cathodes, and the resulting full batteries delivered an outstanding capacity of 336 mAh g-1 at 0.1 A g-1 and exhibited impressive long-term reversibility with a capacity retention of 78.7% for 2000 cycles. The proposed coating strategy is viable for developing porous structures with cutting-edge designs and for textured surface engineering.

High-Performance Graphene Biocomposite Enabled by Fe3+ Coordination for Thermal Management.

Emerging biocomposites with excellent heat dissipation capabilities and inherent sustainability are urgently needed to address the cooling issues of modern electronics and growing environmental concerns. However, the moisture stability, mechanical performance, thermal conductivity, and even flame retardancy of biomass-based materials are generally insufficient for practical thermal management applications. Herein, we present a high-performance graphene biocomposite consisting of carboxylated cellulose nanofibers and graphene nanosheets through an evaporation-induced self-assembly and subsequent Fe3+ cross-linking strategy. The Fe3+ coordination plays a critical role in stabilizing the material structure, thereby improving the mechanical strength and water stability of the biocomposite films, and its effect is revealed by density functional theory calculations. The hierarchical structure of the biocomposite films also leads to a high in-plane thermal conductivity of 42.5 W m-1 K-1, enabling a superior heat transfer performance. Furthermore, the resultant biocomposite films exhibit outstanding Joule heating performance with a fast thermal response and long-term stability, improved thermal stability, and flame retardancy. Therefore, such a general strategy and the desired overall properties of the biocomposite films offer wide application prospects for functional and safe thermal management.

Highly Thermoconductive, Strong Graphene-Based Composite Films by Eliminating Nanosheets Wrinkles.

Graphene-based thermally conductive composites have been proposed as effective thermal management materials for cooling high-power electronic devices. However, when flexible graphene nanosheets are assembled into macroscopic thermally conductive composites, capillary forces induce shrinkage of graphene nanosheets to form wrinkles during solution-based spontaneous drying, which greatly reduces the thermal conductivity of the composites. Herein, graphene nanosheets/aramid nanofiber (GNS/ANF) composite films with high thermal conductivity were prepared by in-plane stretching of GNS/ANF composite hydrogel networks with hydrogen bonds and π-π interactions. The in-plane mechanical stretching eliminates graphene nanosheets wrinkles by suppressing inward shrinkage due to capillary forces during drying and achieves a high in-plane orientation of graphene nanosheets, thereby creating a fast in-plane heat transfer channel. The composite films (GNS/ANF-60 wt%) with eliminated graphene nanosheets wrinkles showed a significant increase in thermal conductivity (146 W m-1 K-1) and tensile strength (207 MPa). The combination of these excellent properties enables the GNS/ANF composite films to be effectively used for cooling flexible LED chips and smartphones, showing promising applications in the thermal management of high-power electronic devices.

Organic molecule-assisted intermediate adsorption for conversion of CO2 to CO by electrocatalysis.

Currently, Zn-based catalysts for electrochemical CO2 reduction reactions are limited by their moderate carbophilicity, resulting in low catalytic activity and CO selectivity. To this end, we selected 5-mercapto-1-methylimidazole, a small molecule that possesses the ability to both coordinate to Zn and interact with the intermediates, to modify electrochemically deposited Zn nanosheets. The interaction between them effectively enhances intermediate adsorption by lowering the Gibbs free energy, which leads to an increase of the Faraday efficiency to 1.9 times and the CO partial current density to 3.0 times that of the pristine sample (-1.0 V vs. RHE).

Adjusting zinc deposition behaviors by a modified separator to acquire zinc anodes for aqueous rechargeable zinc-ion batteries.

Aqueous rechargeable zinc ion batteries (ARZIBs) are ideal for massive and longstanding energy storage applications because of their excellent security and low operation cost. Nevertheless, ARZIBs are subject to the severe corrosion reaction of zinc metal anodes that is derived from the thermodynamic unsteadiness of the zinc anodes in aqueous solution, as well as zinc dendrite growth originating from uncontrolled zinc deposition. Herein, we created a separator by coating a thin piece of polypropylene (PP) with a compound consisting of zinc trifluoromethanesulfonate [Zn(OTf)2] and poly(vinylidene fluoride-hexafluoropropylene (PVDF-HFP). Consequently, the severe corrosion reaction of the zinc metal anodes and the profuse formation of zinc dendrites were effectively mitigated by the novel PP separator, which prolonged the lifetime of the zinc metal anodes. When a zinc metal plating layer was used with preferential (002) crystallographic orientation, the cyclic performance over 1100 h of the symmetrical Zn∥Zn battery based on the novel separator was steady. Additionally, the Zn∥MnO2 batteries exhibited an impressive specific capacity and competitive long durability of 75.5% over 500 cycles at a current density of 0.1 A g-1. With this work, we intend to set the standard for designing novel separators in the construction of advanced zinc anodes for high-performance ARZIBs.

Self-Catalytic Ternary Compounds for Efficient Synthesis of High-Quality Boron Nitride Nanotubes.

The large-scale synthesis of high-quality boron nitride nanotubes (BNNTs) has attracted considerable interests due to their applications in nanocomposites, thermal management, and so on. Despite decades of development, efficient preparation of high-quality BNNTs, which relies on the effective design of precursors and catalysts and deep insights into the catalytic mechanisms, is still urgently needed. Here, a self-catalytic process is designed to grow high-quality BNNTs using ternary W-B-Li compounds. W-B-Li compounds provide boron source and catalyst for BNNTs growth. High-quality BNNTs are successfully obtained via this approach. Density functional theory-based molecular dynamics (DFT-MD) simulations demonstrate that the Li intercalation into the lattice of W2 B5 promotes the formation of W-B-Li liquid and facilitates the compound evaporation for efficient BNNTs growth. This work demonstrates a high-efficient self-catalytic growth of high-quality BNNTs via ternary W-B-Li compounds, providing a new understanding of high-quality BNNTs growth.

Interface Engineering of Aqueous Zinc/Manganese Dioxide Batteries with High Areal Capacity and Energy Density.

Commercialization of aqueous batteries is mainly hampered by their low energy density, owing to the low mass loading of active cathode materials. In this work, a MnO2 cathode structure (MnO2 /CTF) is designed to modify the MnO2 /collector interface for enhanced ion transportation properties. Such a cathode can achieve ultrahigh mass loading of MnO2 , large areal capacity, and high energy density, with excellent cycling stability and rate performance. Specifically, a 0.15 mm thick MnO2 /CTF cathode can realize a mass loading of 20 mg cm-2 with almost 100% electrochemical conversion of MnO2 , providing the maximum areal capacity of 12.08 mA h cm-2 and energy density of 191 W h kg-1 for Zn-MnO2 /CTF batteries when considering both cathode and anode. Besides the conventional low energy demonstrations, such a Zn-MnO2 /CTF battery is capable of realistic applications, such as mobile phones in our daily life, which is a promising alternative for wearable electronics.

Bridge-type 1D/2D boron nitride enhances the thermal management capability of polymer composites.

We propose an efficient strategy based on the electrospinning technique combined with multi-dimensional fillers to fabricate composites with well-established thermal pathways. A bridge-type structure is constructed in the composite fibers by integrating 1D boron nitride nanofibers and 2D boron nitride nanosheets, which can accelerate the formation of a valid thermal network, thereby the BNNS/BNNF/polyacrylonitrile (bsf) composites perform better than the BNNS/polyacrylonitrile (bs) composites. This strategy can be extended to the preparation of other electrospun 1D/2D nanofiller/polymer composite fiber films.

Local environment-mediated efficient electrocatalysis of CO2 to CO on Zn nanosheets.

Nowadays, the goal of carbon peaking and carbon neutrality has become a global consensus, and electrochemical CO2 reduction to provide high-value power fuel is one of the major technical approaches attracting significant research interests and application prospects. However, the inevitable hydrogen evolution reaction in water-based electrolyte systems crowds out the reactive sites of active metals, causing a low CO2 conversion efficiency. In this work, Zn nanosheets were prepared via electrodeposition on the surface of carbon paper and then modified with polytetrafluoroethylene (PTFE) to tune the wetting angle of the electrolyte. A CO faradaic efficiency of 90.2% was achieved for Zn NS-8% PTFE (contact angle: 136.8°) at the electrolytic voltage of -1.0 V vs. RHE along with an overall current density of -7.9 mA cm-2. Experimental results and molecular dynamics simulation revealed that PTFE weakened the aggregation of H2O molecules and was more beneficial for capturing and adsorbing CO2 molecules near the electrode surface. The active sites of hydrogen production were transformed into the reaction center for electrocatalytic CO2 reduction due to the hydrophobicity of the electrode, and the accumulation of the local CO2 concentration accelerated the kinetic activity for electrochemical conversion (CO2 to CO). This strategy of tuning the local environment offers an alternative approach for effective electrode manufacturing in liquid electrolytes.

Surfactant-modified Zn nanosheets on carbon paper for electrochemical CO2 reduction to CO.

We report a strategy that tunes the CO2 and proton concentrations near the electrode-electrolyte interface using surfactant modification with various amounts (0.05, 0.8, 1.6, and 3.2 mg) of hexadecyl trimethyl ammonium bromide (CTAB). The positively charged group of CTAB favors CO2 surface diffusion and inhibits excessive proton accumulation on Zn nanosheets on carbon paper. A CO faradaic efficiency of 95.6% and a total ampere density of -13.1 mA cm-2 were obtained over the optimal CTAB-modified Zn electrode at -1.1 V with stability over 12 hours.

Freestanding Metal-Organic Frameworks and Their Derivatives: An Emerging Platform for Electrochemical Energy Storage and Conversion.

Metal-organic frameworks (MOFs) have recently emerged as ideal electrode materials and precursors for electrochemical energy storage and conversion (EESC) owing to their large specific surface areas, highly tunable porosities, abundant active sites, and diversified choices of metal nodes and organic linkers. Both MOF-based and MOF-derived materials in powder form have been widely investigated in relation to their synthesis methods, structure and morphology controls, and performance advantages in targeted applications. However, to engage them for energy applications, both binders and additives would be required to form postprocessed electrodes, fundamentally eliminating some of the active sites and thus degrading the superior effects of the MOF-based/derived materials. The advancement of freestanding electrodes provides a new promising platform for MOF-based/derived materials in EESC thanks to their apparent merits, including fast electron/charge transmission and seamless contact between active materials and current collectors. Benefiting from the synergistic effect of freestanding structures and MOF-based/derived materials, outstanding electrochemical performance in EESC can be achieved, stimulating the increasing enthusiasm in recent years. This review provides a timely and comprehensive overview on the structural features and fabrication techniques of freestanding MOF-based/derived electrodes. Then, the latest advances in freestanding MOF-based/derived electrodes are summarized from electrochemical energy storage devices to electrocatalysis. Finally, insights into the currently faced challenges and further perspectives on these feasible solutions of freestanding MOF-based/derived electrodes for EESC are discussed, aiming at providing a new set of guidance to promote their further development in scale-up production and commercial applications.

Nanomaterials enhancing the solid-state storage and decomposition of ammonia.

Hydrogen is ideal for producing carbon-free and clean-green energy with which to save the world from climate change. Proton exchange membrane fuel cells use to hydrogen to produce 100% clean energy, with water the only by-product. Apart from generating electricity, hydrogen plays a crucial role in hydrogen-powered vehicles. Unfortunately, the practical uses of hydrogen energy face many technical and safety barriers. Research into hydrogen generation and storage and reversibility transportation are still in its very early stages. Ammonia (NH3) has several attractive attributes, with a high gravimetric hydrogen density of 17.8 wt% and theoretical hydrogen conversion efficiency of 89.3%. Ammonia storage and transport are well-established technologies, making the decomposition of ammonia to hydrogen the safest and most carbon-free option for using hydrogen in various real-time applications. However, several key challenges must be addressed to ensure its feasibility. Current ammonia decomposition technologies require high temperatures, pressures and non-recyclable catalysts, and a sustainable decomposition mechanism is urgently needed. This review article comprehensively summarises current knowledge about and challenges facing solid-state storage of ammonia and decomposition. It provides potential strategic solutions for developing a scalable process with which to produce clean hydrogen by eliminating possible economic and technical barriers.

Advanced Multifunctional Aqueous Rechargeable Batteries Design: From Materials and Devices to Systems.

Multifunctional aqueous rechargeable batteries (MARBs) are regarded as safe, cost-effective, and scalable electrochemical energy storage devices, which offer additional functionalities that conventional batteries cannot achieve, which ideally leads to unprecedented applications. Although MARBs are among the most exciting and rapidly growing topics in scientific research and industrial development nowadays, a systematic summary of the evolution and advances in the field of MARBs is still not available. Therefore, the review presented comprehensively and systematically summarizes the design principles and the recent advances of MARBs by categories of smart ARBs and integrated systems, together with an analysis of their device design and configuration, electrochemical performance, and diverse smart functions. The two most promising strategies to construct novel MARBs may be A) the introduction of functional materials into ARB components, and B) integration of ARBs with other functional devices. The ongoing challenges and future perspectives in this research and development field are outlined to foster the future development of MARBs. Finally, the most important upcoming research directions in this rapidly developing field are highlighted that may be most promising to lead to the commercialization of MARBs and to a further broadening of their range of applications.

CoNiO2 /Co4 N Heterostructure Nanowires Assisted Polysulfide Reaction Kinetics for Improved Lithium-Sulfur Batteries.

The "shuttle effect" of soluble polysulfides and slow reaction kinetics hinder the practical application of Li-S batteries. Transition metal oxides are promising mediators to alleviate these problems, but the poor electrical conductivity limits their further development. Herein, the homogeneous CoNiO2 /Co4 N nanowires have been fabricated and employed as additive of graphene based sulfur cathode. Through optimizing the nitriding degree, the continuous heterostructure interface can be obtained, accompanied by effective adjustment of energy band structure. By combining the strong adsorptive and catalytic properties of CoNiO2 and electrical conductivity of Co4 N, the in situ formed CoNiO2 /Co4 N heterostructure reveals a synergistic enhancement effect. Theoretical calculation and experimental design show that it can not only significantly inhibit "shuttle effect" through chemisorption and catalytic conversion of polysulfides, but also improve the transport rate of ions and electrons. Thus, the graphene composite sulfur cathode supported by these CoNiO2 /Co4 N nanowires exhibits improved sulfur species reaction kinetics. The corresponding cell provides a high rate capacity of 688 mAh g-1 at 4 C with an ultralow decaying rate of ≈0.07% per cycle over 600 cycles. The design of heterostructure nanowires and graphene composite structure provides an advanced strategy for the rapid capture-diffusion-conversion process of polysulfides.

Unique Arrangement of Atoms Leads to Low Thermal Conductivity: A Comparative Study of Monolayer Mg2C.

Two-dimensional Mg2C, one of the typical representative MXene materials, is attracting lots of attention due to its outstanding properties. In this study, we find the thermal conductivity of monolayer Mg2C is more than 2 orders of magnitude lower than graphene and is even lower than MoS2 despite the relatively lighter atoms of Mg and C. Based on the comparative analysis with graphene, silicene, and MoS2, the underlying mechanism is found lying in the unique arrangement of atoms (lighter atoms in the middle plane) and large electronegativity difference in Mg2C. The phonon anharmonicity is strong due to the resonant bonding. In addition, dual band gaps emerge in the phonon dispersion of Mg2C, which limit the phonon-phonon scattering and reduce the phonon relaxation time. This study reveals a new mechanism responsible for low thermal conductivity, which would be helpful for designing thermal functional materials and pave the way for applications in thermoelectrics.