Understanding the Highly Reversible Potassium Storage of Hollow Ternary (Bi-Sb)2S3@N-C Nanocube.

Metal sulfide anodes have aroused much attention in potassium ion batteries (PIBs) owing to their high theoretical capacities, but the sluggish kinetics and inferior cycling performance caused by severe volumetric change and particle pulverization greatly hinder their further development. Herein, robust hollow structure design together with phase structure engineering endow (Bi-Sb)2S3@N-C anode with superior (de)potassiation kinetics and excellent electrochemical performances in PIBs. Specifically, in situ X-ray diffraction combined with density functional theory calculations and ex situ X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy (TEM) analyses indicated a fresh reaction mechanism of (Bi-Sb)2S3 anode with a distinctive multistep (de)potassiation route along (003) plane of (Bi,Sb) alloy thanks to the Bi-Sb phase regulation in (Bi-Sb)2S3 anode, ensuring it with superior reaction kinetics. Moreover, in situ TEM characterization revealed the advantages of the hollow nanostructure with carbon shell, facilitating fast ion transport kinetics and high tolerance of volume change as well as enabling the structural integrity of electrode material during (de)potassiation. As a result, the (Bi-Sb)2S3 hollow nanocube with N-doped carbon shell ((Bi-Sb)2S3@N-C) delivers a high initial Coulombic efficiency of 66.3%, a great rate performance of 289 mAh g-1 at 2.0 A g-1, and an ultralong cycling life (89% retention after 220 cycles at 0.1 A g-1 and 85% retention after 1600 cycles at 2.0 A g-1) in PIBs. Furthermore, the full cell of (Bi-Sb)2S3@N-C//PTCDA affords a high reversible capacity of 281 mA h g-1 at 1.0 A g-1 after 300 cycles. This work combines structural design and in situ techniques, proving a successful nanostructure engineering strategy to rationalize alloy-type electrode materials for PIBs.

Interface-Modulated Resistive Switching in Mo-Irradiated ReS2 for Neuromorphic Computing.

Coupling charge impurity scattering effects and charge-carrier modulation by doping can offer intriguing opportunities for atomic-level control of resistive switching (RS). Nonetheless, such effects have remained unexplored for memristive applications based on 2D materials. Here a facile approach is reported to transform an RS-inactive rhenium disulfide (ReS2 ) into an effective switching material through interfacial modulation induced by molybdenum-irradiation (Mo-i) doping. Using ReS2 as a model system, this study unveils a unique RS mechanism based on the formation/dissolution of metallic ß-ReO2 filament across the defective ReS2 interface during the set/reset process. Through simple interfacial modulation, ReS2 of various thicknesses are switchable by modulating the Mo-irradiation period. Besides, the Mo-irradiated ReS2 (Mo-ReS2 ) memristor further exhibits a bipolar non-volatile switching ratio of nearly two orders of magnitude, programmable multilevel resistance states, and long-term synaptic plasticity. Additionally, the fabricated device can achieve a high MNIST learning accuracy of 91% under a non-identical pulse train. The study's findings demonstrate the potential for modulating RS in RS-inactive 2D materials via the unique doping-induced charged impurity scattering property.

Wafer-Scale 2D Hafnium Diselenide Based Memristor Crossbar Array for Energy-Efficient Neural Network Hardware.

Memristor crossbar with programmable conductance could overcome the energy consumption and speed limitations of neural networks when executing core computing tasks in image processing. However, the implementation of crossbar array (CBA) based on ultrathin 2D materials is hindered by challenges associated with large-scale material synthesis and device integration. Here, a memristor CBA is demonstrated using wafer-scale (2-inch) polycrystalline hafnium diselenide (HfSe2 ) grown by molecular beam epitaxy, and a metal-assisted van der Waals transfer technique. The memristor exhibits small switching voltage (0.6 V), low switching energy (0.82 pJ), and simultaneously achieves emulation of synaptic weight plasticity. Furthermore, the CBA enables artificial neural network with a high recognition accuracy of 93.34%. Hardware multiply-and-accumulate (MAC) operation with a narrow error distribution of 0.29% is also demonstrated, and a high power efficiency of greater than 8-trillion operations per second per Watt is achieved. Based on the MAC results, hardware convolution image processing can be performed using programmable kernels (i.e., soft, horizontal, and vertical edge enhancement), which constitutes a vital function for neural network hardware.

Unlocking Rapid and Robust Sodium Storage Performance of Zinc-Based Sulfide via Indium Incorporation.

Zinc sulfide (ZnS) exhibits promise in sodium-ion batteries (SIBs) because of its low operation voltage and high theoretical specific capacity. However, pristine ZnS is not adequate in realizing rapid and robust sodium storage owing to its low reversibility, poor structure stability, and sluggish kinetics. To date, most efforts focus on utilizing carbonaceous incorporation to improve its electrochemical performances. Nevertheless, it remains an arduous challenge for realizing superior rate capability while obtaining stable cycling. Herein, inspired by the crystal structure of hexagonal ZnIn2S4, which possesses an intrinsic layered feature with larger unit-cell volume versus that of ZnS, indium incorporation is thus deployed as an immediate remedy. In/ex situ investigations combined with density functional theory calculations are conducted to reveal the superior kinetics, high reversibility, and good structure stability of ZnIn2S4. Notably, the formed indium-based derivatives during cycling manifest a Na+ (de)intercalation process, thereby exciting a synergetic mechanism to stabilize electrochemical cycling. As a result, the electrochemical performances of Zn-based sulfide are significantly improved via the indium incorporation. Furthermore, a full cell based on the ZnIn2S4 anode with the superior electrochemical performance is developed. This work provides an effective tactic of heteroatom incorporation for optimizing structure as well as exciting a complementary reaction process toward developing superior anodes for high-performance alkali-ion batteries.

Nanoframes@CNT Beads-on-a-String Structures: Toward an Advanced High-Stable Sodium-Ion Full Battery.

Engineering intriguing electrode with exceptional kinetics behaviors is imperative for boosting sodium storage systems. Herein, the uniform nanoframes are threaded by the interwoven carbon nanotube (CNT) conductive network to form an ingenious beads-on-a-string structured NiFePBA nanoframe/CNT (NFPB-NF/CNT) cathode and the corresponding derivative NiFeSe nanoframe/CNT (NFS-NF/CNT) anode. NFPB-NF/CNT exhibited remarkable cycling life along with outstanding rate capability and low voltage decay per cycle. The fast Na+ conduction and sufficient sodiation reaction is proved using Na+ diffusion models. Meanwhile, an exceptional sodium storage capacity and prolonged cycling life is achieved using binary NFS-NF/CNT anode at a high rate. In situ and ex situ investigations are used to reveal the sodium storage mechanisms and structural evolution process. Furthermore, a sodium-ion full battery based on the above electrodes shows stable performance accompanied by high energy conversion efficiency. The material design strategy provides a new solution for exploiting smart multicomponent composites toward advanced energy storage devices.

Microstructural Engineering of Cathode Materials for Advanced Zinc-Ion Aqueous Batteries.

Zinc-ion batteries (ZIBs) have attracted intensive attention due to the low cost, high safety, and abundant resources. However, up to date, challenges still exist in searching for cathode materials with high working potential, excellent electrochemical activity, and good structural stability. To address these challenges, microstructure engineering has been widely investigated to modulate the physical properties of cathode materials, and thus boosts the electrochemical performances of ZIBs. Here, the recent research efforts on the microstructural engineering of various ZIB cathode materials are mainly focused upon, including composition and crystal structure selection, crystal defect engineering, interlayer engineering, and morphology design. The dependency of cathode performance on aqueous electrolyte for ZIB is further discussed. Finally, future perspectives and challenges on microstructure engineering of cathode materials for ZIBs are provided. It is aimed to provide a deep understanding of the microstructure engineering effect on Zn2+ storage performance.

Controllable Synthesis of Two-Dimensional Molybdenum Disulfide (MoS2 ) for Energy-Storage Applications.

Lamellar molybdenum disulfide (MoS2 ) has attracted a wide range of research interests in recent years because of its two-dimensional layered structure, ultrathin thickness, large interlayer distance, adjustable band gap, and capability to form different crystal structures. These special characteristics and high anisotropy have made MoS2 widely applicable in energy storage and harvesting. In this Minireview, a systematic and comprehensive introduction to MoS2 , as well as its composites, is presented. It is aimed to summarize the various synthetic methods of MoS2 -based composites and their application in energy-storage devices (lithium-ion batteries, sodium-ion batteries, lithium-sulfur batteries, and supercapacitors) in detail. Based on recent studies, this Minireview provides important and comprehensive guidelines for further study and development efforts in the MoS2 in energy-storage field.

Design Multifunctional Catalytic Interface: Toward Regulation of Polysulfide and Li2 S Redox Conversion in Li-S Batteries.

The polysulfide shuttle effect and sluggish reaction kinetics hamper the practical applications of lithium-sulfur (Li-S) batteries. Incorporating a functional interlayer to trapping and binding polysulfides has been found effective to block polysulfide migration. Furthermore, surface chemistry at soluble polysulfides/electrolyte interface is a crucial step for Li-S battery in which stable cycling depends on adsorption and reutilization of blocked polysulfides in the electrolyte. A multifunctional catalytic interface composed of niobium nitride/N-doped graphene (NbN/NG) along the soluble polysulfides/electrolyte is designed and constructed to regulate corresponding interface chemical reaction, which can afford long-range electron transfer surfaces, numerous strong chemisorption, and catalytic sites in a working lithium-sulfur battery. Both experimental and theoretical calculation results suggest that a new catalytic interface enabled by metal-like NbN with superb electrocatalysis anchored on NG is highly effective in regulating the blocked polysulfide redox reaction and tailoring the Li2 S nucleation-growth-decomposition process. Therefore, the Li-S batteries with multifunctional NbN/NG barrier exhibit excellent rate performance (621.2 mAh g-1 at 3 C) and high stable cycling life (81.5% capacity retention after 400 cycles). This work provides new insights to promote Li-S batteries via multifunctional catalytic interface engineering.

High-Concentration Niobium-Substituted WS2 Basal Domains with Reconfigured Electronic Band Structure for Hydrogen Evolution Reaction.

Extrinsically controlling the intrinsic activity and stability of two-dimensional (2D) semiconducting materials by substitutional doping is crucial for energy-related applications. However, an in situ transition-metal doping strategy for uniform and large-area chemical vapor deposited 2D semiconductors remains a formidable challenge. Here, we successfully synthesize highly uniform niobium-substituted tungsten disulfide (Nb-WS2) monolayers, with a doping concentration of nearly 7% and sizes reaching 100 µm, through a metal dopant precursor route, using salt-catalyzed chemical vapor deposition (CVD). Our results reveal unusual effects in the structural, optical, electronic, and electrocatalysis characteristics of the Nb-WS2 monolayer. The Nb dopants readily induce a band restructuring effect, providing the most active site with a hydrogen adsorption energy of 0.175 eV and hence greatly improving its hydrogen evolution activity. The combined advantages of the unusual physics and chemistry by in situ CVD doping technique open the possibility in designing 2D-material-based electronics and catalysts of novel functionalities.

Polypyrrole coated niobium disulfide nanowires as high performance electrocatalysts for hydrogen evolution reaction.

Developing an environmentally friendly and low-cost approach to improve electrocatalytic activity for hydrogen evolution reaction (HER) has drawn wide attention due to its significant value and challenge. NbS2-based materials exhibit high performance catalytic activity in electrochemical area, but its poor stability and synthetic difficulty limits its development and application. This work reports on the enhancement of HER performance through the utilization of conductive polymer polypyrrole (Ppy) on NbS2 nanowires as electrocatalysts, which can be easily prepared. The Ppy coated NbS2 nanowires obtain excellent catalytic activity for HER with low onset potential (-56 mV) and much lower overpotential (-219 mV) at a current of -10 mA cm-2 compared with bare NbS2 nanowires.

Thermal-Assisted Vertical Electron Injections in Few-Layer Pyramidal-Structured MoS2 Crystals.

The interlayer screening effects and charge conduction mechanisms in atomically thin two-dimensional (2D) materials are crucial for electronics and optoelectronics applications. However, such effects remain largely unexplored in chemical vapor deposition (CVD)-grown molybdenum disulfide (MoS2) crystals. Here, we report a controllable CVD-grown monolayer MoS2 and layer-by-layer pyramidal-structured MoS2 crystals with an oxidized Mo foil precursor. The interlayer screening effects and charge conduction mechanisms in the pyramidal-structured MoS2 crystals are studied. Although the Fowler-Nordheim (FN) tunneling model is widely adopted to describe the vertical charge transport mechanism at the 2D semiconductor/bulk metal interface, we found that such a mechanism cannot satisfactorily explain the electrical measurement obtained from our CVD-grown MoS2 samples. Instead, our analysis reveals that Richardson-Schottky (RS) emission is the dominant transport mechanism when Vbias < 1 V. Our findings provide a fundamental understanding of the charge conduction mechanism in CVD-grown MoS2 crystals, which is crucial for development of MoS2 electronics and optoelectronics devices.

Location-selective growth of two-dimensional metallic/semiconducting transition metal dichalcogenide heterostructures.

An electrical contact between metallic electrodes and semiconductors is critical for the performance of electronic and optoelectronic devices. Two-dimensional (2D) transition metal dichalcogenides (TMDs) contain semiconducting, metallic and insulating material members, which enables the fabrication of highly integrated electronic devices fully based on 2D TMDs. However, location-selective synthesis of metallic/semiconducting heterostructures by a chemical vapor deposition (CVD) method has rarely been reported. In this study, a two-step CVD method was applied to fabricate 2D metallic/semiconducting heterostructures. Semiconducting WS2 was first synthesized and served as the template for the following CVD growth of metallic NbS2. In the growth process, NbS2 flakes selectively nucleate at the edges of WS2 monolayers, thus resulting in the formation of NbS2 islands circling around the WS2 monolayers. The as-grown NbS2/WS2 heterostructure was further systematically characterized by Raman spectroscopy, atomic force microscopy (AFM) and scanning transition electron microscopy (STEM). The NbS2 layers epitaxially grown on the WS2 monolayers exhibit a 3R phase and there was no discernible lattice strain in the NbS2/WS2 van der Waals (vdW) heterostructure. The growth of the metallic/semiconducting 2D heterostructures could benefit the nanoelectronic device fabrication and provide a platform for the 2D contact resistance study.

Boosting Sodium Storage of Fe1-xS/MoS2 Composite via Heterointerface Engineering.

Improving the cycling stability of metal sulfide-based anode materials at high rate is of great significance for advanced sodium ion batteries. However, the sluggish reaction kinetics is a big obstacle for the development of high-performance sodium storage electrodes. Herein, we have rationally engineered the heterointerface by designing the Fe1-xS/MoS2 heterostructure with abundant "ion reservoir" to endow the electrode with excellent cycling stability and rate capability, which is proved by a series of in and ex situ electrochemical investigations. Density functional theory calculations further reveal that the heterointerface greatly decreases sodium ion diffusion barrier and facilitates charge-transfer kinetics. Our present findings not only provide a deep analysis on the correlation between the structure and performance, but also draw inspiration for rational heterointerface engineering toward the next-generation high-performance energy storage devices.

Effects of precursor pre-treatment on the vapor deposition of WS2 monolayers.

Transition metal oxide powders have been widely used as the growth precursors for monolayer transition metal dichalcogenides (TMDCs) in chemical vapor deposition (CVD). It has been proposed that metal oxide precursors in the gas phase undergo a two-step reaction during CVD growth, where transition metal sub-oxides are likely formed first and then the sulfurization of these sub-oxides leads to the formation of TMDCs. However, the effects of stoichiometry of transition metal oxide precursors on the growth of TMDC monolayers have not been studied yet. In this contribution, we report the critical role of the WO3 precursor pre-annealing process on the growth of WS2 monolayers. Besides, several WO3 precursors with different types of oxygen vacancies have also been prepared and investigated by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and density functional theory calculation. Among all the non-stoichiometric WO3 precursors, thermally annealed WO3 powder exhibits the highest oxygen vacancy concentration and produces WS2 monolayers with significantly improved quality in terms of lateral size, density, and crystallinity. Our comprehensive study suggests that the chemical composition of transition metal oxide precursors would be fundamentally critical for the growth of large-area and high-quality WS2 monolayers, which further pave the way for revealing their intrinsic properties and unique applications.

Mechanism Investigation of High-Performance Li-Polysulfide Batteries Enabled by Tungsten Disulfide Nanopetals.

Understanding the reaction kinetics and mechanism of Li-polysulfide batteries is critical in designing advanced host materials for improved performance. However, up to now, the reaction mechanism within the Li-polysulfide batteries is still unclear. Herein, we study the reaction mechanism of a high-performance Li-polysulfide battery by in situ X-ray diffraction (XRD) and density functional theory (DFT) calculations based on a multifunctional host material composed of WS2 nanopetals embedded in rGO-CNT (WS2-rGO-CNT) aerogel. The WS2 nanopetal serves as a "catalytic center" to chemically bond the polysulfides and accelerate the polysulfide redox reactions, and the 3D porous rGO-CNT scaffold provides fast and efficient e-/Li+ transportation. Thus, the resulting WS2-rGO-CNT aerogel accommodating the polysulfide catholyte enables a stable cycling performance, excellent rate capability (614 mAh g-1 at 2 C), and a high areal capacity (6.6 mAh cm-2 at 0.5 C). In situ XRD results reveal that the Li2S starts to form at an early stage of discharge (at a depth of 25% of the lower voltage plateau) during the discharge process, and ß-S8 nucleation begins before the upper voltage plateau during the recharge process, which are different from the conventional Li-S battery. Moreover, the WS2 itself could be lithiated/delithiated during the cycling, making the lithiated WS2 (Li xWS2, 0 ≤ x ≤ 0.3) a real host material for Li-polysulfide batteries. DFT calculations suggest that Li xWS2 (0 ≤ x ≤ 0.3) exhibits moderate binding/anchoring interactions toward polysulfides with adsorption energies of 0.51-1.4 eV. Our work reveals the reaction mechanism of the Li-polysulfide batteries and indicates that the lithiated host plays an important role in trapping the polysulfides.

Tailoring NiO Nanostructured Arrays by Sulfate Anions for Sodium-Ion Batteries.

In this contribution, a novel sulfate-ion-controlled synthesis is developed to fabricate freestanding nickel hydroxide nanoarrays on Ni substrate. As an inorganic morphology-controlled agent, SO42- ions play a critical role in controlling the crystal growth and the nanoarray morphologies, by modulating the growth rate of adsorbed crystal facets or inserting into the metal hydroxide interlayers. By controlling the SO42- concentration, the nanostructured arrays are tailored from one-dimensional (1D) Ni(SO4 )0.3 (OH)1.4 nanobelt arrays to hierarchical ß-Ni(OH)2 nanosheet arrays. With further graphene oxide modification and postheat treatment, the obtained NiO/graphene hybrid nanoarrays show great potential for high-performance sodium-ion batteries, which exhibit a cyclability of 380 mAh g-1 after undergoing 100 cycles at 0.5 C and reach a rate capability of 335 mA h g-1 at 10 C.

Significant photoluminescence enhancement in WS2 monolayers through Na2S treatment.

Tungsten disulfide monolayers have attracted extensive attention in nanoelectronics and optoelectronics applications due to their remarkable electronic and optical properties. High-quality WS2 monolayers with a scalable size and uniform thickness can be synthesized by a chemical vapor deposition method (CVD). However, they commonly contain intrinsic structural defects and different populations of charge carriers, which are responsible for different contributions of excitons, trions, and biexcitons to their photoluminescence (PL) emission. Here, we adopt sodium sulphide (Na2S) solution to chemically treat CVD-grown WS2 monolayers by a simple immersing method. The results show that WS2 monolayers have a significantly enhanced PL emission by a factor of 25-fold and an obvious red-shift of the PL wavelength, resulting from the different excitonic states induced by effective n-type doping after Na2S treatment. This work provides a simple but promising chemical doping route to significantly improve the optical properties of WS2 monolayers and paves the way for the realization of practical WS2 monolayer based optoelectronic applications.