High-Efficiency Rechargeable Fe-CO2 Battery: A Route for Effective CO2 Conversion and Energy Storage.

Because of their high theoretical energy density, metal-CO2 batteries based on Li, Na, or K have attracted increasing attention recently for meeting the growing demands of CO2 recycling and conversion into electrical energy. However, the scarcity of active anode material resources, high cost, as well as safety concerns of Li, Na, and K create obstacles for practical applications. Herein, we demonstrate for the first time a high-efficiency (η = 77.2%) rechargeable Fe-CO2 battery that is composed of iron (Fe) anode and MoS2-catalysts deposited carbon cathode. MoS2 catalysts are crucial to the successful acceleration of reaction kinetics of Fe during charge and discharge with a minimum overpotential of the cell. The Fe-CO2 cell has a higher initial specific capacity of 12,500 mA h g-1 with an average discharge potential of 0.65 V and operates reversibly with a lower overpotential than that of Li-CO2 batteries with a cutoff capacity of 500 mA h g-1. Our Fe-CO2 battery can effectively convert CO2 greenhouse gas into electrical energy by consuming 1 ton of CO2 with usage of 1.23 tons of iron.

Effect of morphological variation in three-dimensional multiwall carbon nanotubes as the host cathode material for high-performance rechargeable lithium-sulfur batteries.

Lithium-sulfur batteries (LSBs) demonstrate potential as next-generation energy storage systems due to the high theoretical capacity and energy density of the sulfur cathode (1672 mAh g-1 and 2600 W h kg-1, respectively) in addition to the low-cost, natural abundance, and environmentally benign characteristics of sulfur. However, the insulating nature of sulfur requires an efficient conductive and porous host material such as three-dimensional carbon nanotubes (3D CNTs). Identifying parameters that provide high conduction pathways and short diffusion lengths for Li-ions within the CNT structure is essential for a highly efficient CNT-S cathode in a LSB. Herein, the effect of morphological variation in 3D CNTs as a sulfur host material is studied, and parameters that affect the performance of a CNT-S cathode in LSB are investigated. Four different 3D CNTs are synthesized via the chemical vapor deposition (CVD) technique that vary in specific surface area (SSA), CNT diameter, pore sizes, and porosity. The superior 3D CNT-S (CNT-S-50) cathode, which possessed high surface area and porosity as compared to the rest of the 3D CNT-S cathodes, with ∼38 wt% (6.27 mg cm-2) sulfur loading, demonstrated an areal and specific discharge capacity of 8.70 mAh cm-2 and 1387 mAh g-1 at 0.1C, respectively. Results from this work demonstrate that the combination of high surface area and porosity are two crucial parameters in 3D CNTs as an efficient sulfur host material for LSB cathodes.

Realizing Electronic Synapses by Defect Engineering in Polycrystalline Two-Dimensional MoS2 for Neuromorphic Computing.

Neuromorphic computing based on two-dimensional transition-metal dichalcogenides (2D TMDs) has attracted significant attention recently due to their extraordinary properties generated by the atomic-thick layered structure. This study presents sulfur-defect-assisted MoS2 artificial synaptic devices fabricated by a simple sputtering process, followed by a precise sulfur (S) vacancy-engineering process. While the as-sputtered MoS2 film does not show synaptic behavior, the S vacancy-controlled MoS2 film exhibits excellent synapse with remarkable nonvolatile memory characteristics such as a high switching ratio (∼103), a large memory window, and long retention time (∼104 s) in addition to synaptic functions such as paired-pulse facilitation (PPF) and long-term potentiation (LTP)/depression (LTD). The synaptic device working mechanism of Schottky barrier height modulation by redistributing S vacancies was systemically analyzed by electrical, physical, and microscopy characterizations. The presented MoS2 synaptic device, based on the precise defect engineering of sputtered MoS2, is a facile, low-cost, complementary metal-oxide semiconductor (CMOS)-compatible, and scalable method and provides a procedural guideline for the design of practical 2D TMD-based neuromorphic computing.

Unravelling the Influence of Surface Modification on the Ultimate Performance of Carbon Fiber/Epoxy Composites.

The overall performance of polymer composites depends on not only the intrinsic properties of the polymer matrix and inorganic filler but also the quality of interfacial adhesion. Although many reported approaches have been focused on the chemical treatment for improving interfacial adhesion, the examination of ultimate mechanical performance and long-term properties of polymer composites has been rarely investigated. Herein, we report carbon fiber (CF)/epoxy composites with improved interfacial adhesion by covalent bonding between CFs and the epoxy matrix. This leads to the improved ultimate mechanical properties and enhanced thermal aging performance. Raman mapping demonstrates the formation of an interphase region derived from the covalent bonding between CFs and the epoxy matrix, which enables the uniform fiber distribution and eliminates phase separation during thermal cycling. The covalent attachment of the CF to the epoxy matrix suppresses its migration during temperature fluctuations, preserving the mechanical performance of resulting composites under the thermal aging process. Furthermore, the finite elemental analysis reveals the effectiveness of the chemical treatment of CFs in improving the interfacial strength and toughness of silane-treated CF/epoxy composites. The insight into the mechanical improvement of CF/epoxy composites suggests the high potential of surface modification of inorganic fillers toward polymer composites with tunable properties for different applications.

Characterize traction-separation relation and interfacial imperfections by data-driven machine learning models.

Interfacial mechanical properties are important in composite materials and their applications, including vehicle structures, soft robotics, and aerospace. Determination of traction-separation (T-S) relations at interfaces in composites can lead to evaluations of structural reliability, mechanical robustness, and failures criteria. Accurate measurements on T-S relations remain challenging, since the interface interaction generally happens at microscale. With the emergence of machine learning (ML), data-driven model becomes an efficient method to predict the interfacial behaviors of composite materials and establish their mechanical models. Here, we combine ML, finite element analysis (FEA), and empirical experiments to develop data-driven models that characterize interfacial mechanical properties precisely. Specifically, eXtreme Gradient Boosting (XGBoost) multi-output regressions and classifier models are harnessed to investigate T-S relations and identify the imperfection locations at interface, respectively. The ML models are trained by macroscale force-displacement curves, which can be obtained from FEA and standard mechanical tests. The results show accurate predictions of T-S relations (R2 = 0.988) and identification of imperfection locations with 81% accuracy. Our models are experimentally validated by 3D printed double cantilever beam specimens from different materials. Furthermore, we provide a code package containing trained ML models, allowing other researchers to establish T-S relations for different material interfaces.

Unusually High Ion Conductivity in Large-Scale Patternable Two-Dimensional MoS2 Film.

The advancement of ion transport applications will require the development of functional materials with a high ionic conductivity that is stable, scalable, and micro-patternable. We report unusually high ionic conductivity of Li+, Na+, and K+ in 2D MoS2 nanofilm exceeding 1 S/cm, which is more than 2 orders of magnitude higher when compared to that of conventional solid ionic materials. The high ion conductivity of different cations can be explained by the mitigated activation energy via percolative ion channels in 2H-MoS2, including the 1D ion channel at the grain boundary, as confirmed by modeling and analysis. We obtain field-effect modulation of ion transport with a high on/off ratio. The ion channel is large-scale patternable by conventional lithography, and the thickness can be tuned down to a single atomic layer. The findings yield insight into the ion transport mechanism of van der Waals solid materials and guide the development of future ionic devices owing to the facile and scalable device fabrication with superionic conductivity.

Asymmetric 2D MoS2 for Scalable and High-Performance Piezoelectric Sensors.

Piezoelectricity in two-dimensional (2D) transition-metal dichalcogenides (TMDs) has attracted significant attention due to their unique crystal structure and the lack of inversion centers when the bulk TMDs thin down to monolayers. Although the piezoelectric effect in atomic-thickness TMDs has been reported earlier, they are exfoliated 2D TMDs and are therefore not scalable. Here, we demonstrate a superior piezoelectric effect from large-scale sputtered, asymmetric 2D MoS2 using meticulous defect engineering based on the thermal-solvent annealing of the MoS2 layer. This yields an output peak current and voltage of 20 pA and 700 mV (after annealing at 450 °C), respectively, which is the highest piezoelectric strength ever reported in 2D MoS2. Indeed, the piezoelectric strength increases with the defect density (sulfur vacancies), which, in turn, increases with the annealing temperature at least up to 450 °C. Moreover, our piezoelectric MoS2 device array shows an exceptional piezoelectric sensitivity of 262 mV/kPa with a high level of uniformity and excellent performance under ambient conditions. A detailed study of the sulfur vacancy-dependent property and its resultant asymmetric structure-induced piezoelectricity is reported. The proposed approach is scalable and can produce advanced materials for flexible piezoelectric devices to be used in emerging bioinspired robotics and biomedical applications.

Stable and high-performance piezoelectric sensor via CVD grown WS2.

Piezoelectric materials are widely used as electromechanical couples for a variety of sensors and actuators in nanoscale electronic devices. The majority of piezoelectric devices display lateral patterning of counter electrodes beside active materials such as two-dimensional transition metal dichalcogenides (2D TMDs). As a result, their piezoelectric output response is strongly dependent on the lattice orientation of the 2D TMD crystal structure, limiting their piezoelectric properties. To overcome this issue, we fabricated a vertical sandwich design of a piezoelectric sensor with a conformal contact to enhance the overall piezoelectric performance. In addition, we enhanced the piezoelectric properties of 2D WS2 by carrying out a unique solvent-vapor annealing process to produce a sulfur-deficient WS2(1-x) structure that yielded a 3-fold higher piezoelectric response voltage (96.74 mV) than did pristine WS2 to a 3 kPa compression. Our device was also found to be stable: it retained its piezoelectric performance even after a month in an ambient atmospheric condition. Our study has revealed a facile methodology for fabricating large-scale piezoelectric devices using an asymmetrically engineered 2D WS2 structure.

Stable and High-Energy-Density Zn-Ion Rechargeable Batteries Based on a MoS2-Coated Zn Anode.

Recently, aqueous Zn-ion rechargeable batteries have drawn increasing research attention as an alternative energy storage system relative to the current Li-ion batteries due to their intrinsic properties of high safety, low cost, and high theoretical volumetric capacity. Nevertheless, unwanted dendrite growth on the Zn anode and unstable cathode materials restrict their practical application. In this study, a unique 2D MoS2 coating on a Zn anode using an electrochemical deposition method has been developed for preventing dendrite growth and intricate side reactions. The coated MoS2 layer is a vertically oriented structure that makes the flow of Zn ions easy with a uniform electric field distribution on the anode, resulting in a uniform stripping and plating of Zn2+. In addition, the MoS2 coating enhances anodic diffusion of Zn ions and reduces the series resistance as confirmed by EIS analysis and therefore improves the overall battery performance. The full cell assembled with the MoS2-Zn anode and MnO2 cathode exhibits an excellent reversible specific capacity of 638 mAh/g at 0.1 A/g and stable cycle performance over 2000 cycles with no dendrite formation at the Zn electrode. The presented MoS2 coating on Zn is a facile, scalable, and promising technology for practical Zn-ion batteries with a long life cycle and high safety.

Nanoengineering to achieve high efficiency practical lithium-sulfur batteries.

Rapidly increasing markets for electric vehicles (EVs), energy storage for backup support systems and high-power portable electronics demand batteries with higher energy densities and longer cycle lives. Among the various electrochemical energy storage systems, lithium-sulfur (Li-S) batteries have the potential to become the next generation rechargeable batteries because of their high specific energy at low cost. However, the development of practical Li-S batteries for commercial products has been challenged by several obstacles, including unstable cycle life and low sulfur utilization. Only a few studies have considered the importance of low electrolyte and high sulfur loading to improve the overall energy densities of Li-S cells. This article reviews the recent developments of Li-S batteries that can meet the benchmarks of practical parameters and exceed the practical energy density of lithium-ion batteries (LIBs) including areal sulfur loading of at least 4 mg cm-2, electrolyte to sulfur ratio of less than 10 µL mg-1, and high cycling stability of over 300 cycles. This review presents the advancements in each component in Li-S batteries, including the enhancement of the electrochemical properties of sulfur cathodes, lithium anodes, or electrolytes. Also identified are several important strategies of nanoengineering and how they address the practical limitations of Li-S batteries to compete against LIBs. Additionally, perspectives on fundamentals, technology, and materials are provided for the development of Li-S batteries based on nanomaterials and nanoengineering so that they can enter the market of high energy density rechargeable storage systems.

Composition-Tunable Synthesis of Large-Scale Mo1- xW xS2 Alloys with Enhanced Photoluminescence.

Alloying two-dimensional transition metal dichalcogenides (2D TMDs) is a promising avenue for band gap engineering. In addition, developing a scalable synthesis process is essential for the practical application of these alloys with tunable band gaps in optoelectronic devices. Here, we report the synthesis of optically uniform and scalable single-layer Mo1- xW xS2 alloys by a two-step chemical vapor deposition (CVD) method followed by a laser thinning process. The amount of W content ( x) in the Mo1- xW xS2 alloy is systemically controlled by the co-sputtering technique. The post-laser process allows layer-by-layer thinning of the Mo1- xW xS2 alloys down to a single-layer; such a layer exhibits tunable properties with the optical band gap ranging from 1.871 to 1.971 eV with variation in the W content, x = 0 to 1. Moreover, the predominant exciton complexes, trions, are transitioned to neutral excitons with increasing W concentration; this is attributed to the decrease in excessive charge carriers with an increase in the W content of the alloy. Photoluminescence (PL) and Raman mapping analyses suggest that the laser-thinning of the Mo1- xW xS2 alloys is a self-limiting process caused by heat dissipation to the substrate, resulting in spatially uniform single-layer Mo1- xW xS2 alloy films. Our findings present a promising path for the fabrication of large-scale single-layer 2D TMD alloys and the design of versatile optoelectronic devices.

Publisher Correction: 2D MoS2 as an efficient protective layer for lithium metal anodes in high-performance Li-S batteries.

In the version of this Article originally published, a technical error in typesetting led to the traces in Fig. 3a being trimmed and made to overlap. The figure has now been corrected with the traces as supplied by the authors; the original and corrected Fig. 3a are shown below. Also, in the last paragraph of the section "Mechanistic study on Li diffusion in MoS2" the authors incorrectly included the term 'high-concentration' in the text "the Li diffusion will be dominated by high-concentration Li migration on the surface of T-MoS2 with a much smaller energy barrier (0.155 eV) to overcome". This term has now been removed from all versions of the Article. Finally, the authors have added an extra figure in the Supplementary Information (Supplementary Fig. 19) to show galvanostatic tests at 1 and 3 mA cm-2 for the MoS2-coated Li symmetric cells. The caption to Fig. 3 of the Article has been amended to reflect this, with the added wording "Galvanostatic tests at 1 and 3 mA cm-2 can be found in Supplementary Fig. 19."

2D MoS2 as an efficient protective layer for lithium metal anodes in high-performance Li-S batteries.

Among the candidates to replace Li-ion batteries, Li-S cells are an attractive option as their energy density is about five times higher (~2,600 Wh kg-1). The success of Li-S cells depends in large part on the utilization of metallic Li as anode material. Metallic lithium, however, is prone to grow parasitic dendrites and is highly reactive to several electrolytes; moreover, Li-S cells with metallic Li are also susceptible to polysulfides dissolution. Here, we show that ~10-nm-thick two-dimensional (2D) MoS2 can act as a protective layer for Li-metal anodes, greatly improving the performances of Li-S batteries. In particular, we observe stable Li electrodeposition and the suppression of dendrite nucleation sites. The deposition and dissolution process of a symmetric MoS2-coated Li-metal cell operates at a current density of 10 mA cm-2 with low voltage hysteresis and a threefold improvement in cycle life compared with using bare Li-metal. In a Li-S full-cell configuration, using the MoS2-coated Li as anode and a 3D carbon nanotube-sulfur cathode, we obtain a specific energy density of ~589 Wh kg-1 and a Coulombic efficiency of ~98% for over 1,200 cycles at 0.5 C. Our approach could lead to the realization of high energy density and safe Li-metal-based batteries.

In situ fabrication of a graphene-coated three-dimensional nickel oxide anode for high-capacity lithium-ion batteries.

The high theoretical specific capacity of nickel oxide (NiO) makes it attractive as a high-efficiency electrode material for electrochemical energy storage. However, its application is limited due to its inferior electrochemical performance and complicated electrode fabrication process. Here, we developed an in situ fabrication of a graphene-coated, three-dimensional (3D) NiO-Ni structure by simple chemical vapor deposition (CVD). We synthesized NiO layers on Ni foam through a thermal oxidation process; subsequently, we grew graphene layers directly on the surface of NiO after a hydrogen-assisted reduction process. The uniform graphene coating renders high electrical conductivity, structural flexibility and high elastic modulus at atomic thickness. The graphene-coated 3D NiO-Ni structure delivered a high areal density of ∼23 mg cm-2. It also exhibits a high areal capacity of 1.2 mA h cm-2 at 0.1 mA cm-2 for its Li-ion battery performance. The high capacity is attributed to the high surface area of the 3D structure and the unique properties of the graphene layers on the NiO anode. Since the entire process is carried out in one CVD system, the fabrication of such a graphene-coated 3D NiO-Ni anode is simple and scalable for practical applications.

Synthesis of uniform single layer WS2 for tunable photoluminescence.

Two-dimensional transition metal dichalcogenides (2D TMDs) have gained great interest due to their unique tunable bandgap as a function of the number of layers. Especially, single-layer tungsten disulfides (WS2) is a direct band gap semiconductor with a gap of 2.1 eV featuring strong photoluminescence and large exciton binding energy. Although synthesis of MoS2 and their layer dependent properties have been studied rigorously, little attention has been paid to the formation of single-layer WS2 and its layer dependent properties. Here we report the scalable synthesis of uniform single-layer WS2 film by a two-step chemical vapor deposition (CVD) method followed by a laser thinning process. The PL intensity increases six-fold, while the PL peak shifts from 1.92 eV to 1.97 eV during the laser thinning from few-layers to single-layer. We find from the analysis of exciton complexes that both a neutral exciton and a trion increases with decreasing WS2 film thickness; however, the neutral exciton is predominant in single-layer WS2. The binding energies of trion and biexciton for single-layer WS2 are experimentally characterized at 35 meV and 60 meV, respectively. The tunable optical properties by precise control of WS2 layers could empower a great deal of flexibility in designing atomically thin optoelectronic devices.

Vertically oriented MoS2 nanoflakes coated on 3D carbon nanotubes for next generation Li-ion batteries.

The advent of advanced electrode materials has led to performance enhancement of traditional lithium ion batteries (LIBs). We present novel binder-free MoS2 coated three-dimensional carbon nanotubes (3D CNTs) as an anode in LIBs. Scanning transmission electron microscopy analysis shows that vertically oriented MoS2 nanoflakes are strongly bonded to CNTs, which provide a high surface area and active electrochemical sites, and enhanced ion conductivity at the interface. The electrochemical performance shows a very high areal capacity of ~1.65 mAh cm-2 with an areal density of ~0.35 mg cm-2 at 0.5 C rate and coulombic efficiency of ~99% up to 50 cycles. The unique architecture of 3D CNTs-MoS2 is indicative to be a promising anode for next generation Li-ion batteries with high capacity and long cycle life.

Centimeter Scale Patterned Growth of Vertically Stacked Few Layer Only 2D MoS2/WS2 van der Waals Heterostructure.

Two-dimensional (2D) van der Waal (vdW) heterostructures composed of vertically-stacked multiple transition metal dichalcogenides (TMDs) such as molybdenum disulfide (MoS2) and tungsten disulfide (WS2) are envisioned to present unprecedented materials properties unobtainable from any other material systems. Conventional fabrications of these hybrid materials have relied on the low-yield manual exfoliation and stacking of individual 2D TMD layers, which remain impractical for scaled-up applications. Attempts to chemically synthesize these materials have been recently pursued, which are presently limited to randomly and scarcely grown 2D layers with uncontrolled layer numbers on very small areas. Here, we report the chemical vapor deposition (CVD) growth of large-area (>2 cm(2)) patterned 2D vdW heterostructures composed of few layer, vertically-stacked MoS2 and WS2. Detailed structural characterizations by Raman spectroscopy and high-resolution/scanning transmission electron microscopy (HRTEM/STEM) directly evidence the structural integrity of two distinct 2D TMD layers with atomically sharp vdW heterointerfaces. Electrical transport measurements of these materials reveal diode-like behavior with clear current rectification, further confirming the formation of high-quality heterointerfaces. The intrinsic scalability and controllability of the CVD method presented in this study opens up a wide range of opportunities for emerging applications based on the unconventional functionalities of these uniquely structured materials.

Three-dimensional free-standing carbon nanotubes for a flexible lithium-ion battery anode.

Flexible lithium-ion batteries (LIBs) have received considerable attention as energy sources for wearable electronics. In recent years, much effort has been devoted to study light-weight, robust, and flexible electrodes. However, high areal and volumetric capacities need to be achieved for practical power and energy densities. In this paper, we report the use of three-dimensional (3D) free-standing carbon nanotubes (CNTs) as a current collector-free anode to demonstrate flexible LIBs with enhanced areal and volumetric capacities. High density CNTs grown on copper (Cu) mesh are transferred to a flexible graphene/polyethylene terephthalate  film and integrated into a flexible LIB. A fully flexible LIB cell integrated with the 3D CNT anode delivers a high areal capacity of 0.25 mAh cm(-2) at 0.1C and shows fairly consistent open circuit voltage under bending. These findings may provide significant advances in the application of flexible LIB based electronic devices.

Highly sensitive wide bandwidth photodetector based on internal photoemission in CVD grown p-type MoS2/graphene Schottky junction.

Two dimensional (2D) Molybdenum disulfide (MoS2) has evolved as a promising material for next generation optoelectronic devices owing to its unique electrical and optical properties, such as band gap modulation, high optical absorption, and increased luminescence quantum yield. The 2D MoS2 photodetectors reported in the literature have presented low responsivity compared to silicon based photodetectors. In this study, we assembled atomically thin p-type MoS2 with graphene to form a MoS2/graphene Schottky photodetector where photo generated holes travel from graphene to MoS2 over the Schottky barrier under illumination. We found that the p-type MoS2 forms a Schottky junction with graphene with a barrier height of 139 meV, which results in high photocurrent and wide spectral range of detection with wavelength selectivity. The fabricated photodetector showed excellent photosensitivity with a maximum photo responsivity of 1.26 AW(-1) and a noise equivalent power of 7.8 × 10(-12) W/√Hz at 1440 nm.

Unusually High Optical Transparency in Hexagonal Nanopatterned Graphene with Enhanced Conductivity by Chemical Doping.

Graphene has received appreciable attention for its potential applications in flexible conducting film due to its exceptional optical, mechanical, and electrical properties. However increasing transmittance of graphene without sacrificing the electrical conductivity has been difficult. The fabrication of optically highly transparent (≈98%) graphene layer with a reasonable electrical conductivity is demonstrated here by nanopatterning and doping. Anodized aluminium oxide nanomask prepared by facile and simple self-assembly technique is utilized to produce an essentially hexagonally nanopatterned graphene. The electrical resistance of the graphene increases significantly by a factor of ≈15 by removal of substantial graphene regions via nanopatterning into hexagonal array pores. However, the use of chemical doping on the nanopatterned graphene almost completely recovers the lost electrical conductivity, thus leading to a desirably much more optically transparent conductor having ≈6.9 times reduced light blockage by graphene material without much loss of electrical conductivity. It is likely that the availability of large number of edges created in the nanopatterned graphene provides ideal sites for chemical dopant attachment, leading to a significant reduction of the sheet resistance. The results indicate that the nanopatterned graphene approach can be a promising route for simultaneously tuning the optical and electrical properties of graphene to make it more light-transmissible and suitable as a flexible transparent conductor.