Artificial LiF-Rich Interface Enabled by In situ Electrochemical Fluorination for Stable Lithium-Metal Batteries.

Lithium (Li)-metal batteries are promising next-generation energy storage systems. One drawback of uncontrollable electrolyte degradation is the ability to form a fragile and nonuniform solid electrolyte interface (SEI). In this study, we propose the use of a fluorinated carbon nanotube (CNT) macrofilm (CMF) on Li metal as a hybrid anode, which can regulate the redox state at the anode/electrolyte interface. Due to the favorable reaction energy between the plated Li and fluorinated CNTs, the metal can be fluorinated directly to a LiF-rich SEI during the charging process, leading to a high Young's modulus (~2.0 GPa) and fast ionic transfer (~2.59×10-7  S cm-1 ). The obtained SEI can guide the homogeneous plating/stripping of Li during electrochemical processes while suppressing dendrite growth. In particular, the hybrid of endowed full cells with substantially enhanced cyclability allows for high capacity retention (~99.3 %) and remarkable rate capacity. This work can extend fluorination technology into a platform to control artificial SEI formation in Li-metal batteries, increasing the stability and long-term performance of the resulting material.

Effective Surface Modification of 2D MXene toward Thermal Energy Conversion and Management.

Thermal energy management is a crucial aspect of many research developments, such as hybrid and soft electronics, aerospace, and electric vehicles. The selection of materials is of critical importance in these applications to manage thermal energy effectively. From this perspective, MXene, a new type of 2D material, has attracted considerable attention in thermal energy management, including thermal conduction and conversion, owing to its unique electrical and thermal properties. However, tailored surface modification of 2D MXenes is required to meet the application requirements or overcome specific limitations. Herein, a comprehensive review of surface modification of 2D MXenes for thermal energy management is discussed. First, this work discusses the current progress in the surface modification of 2D MXenes, including termination with functional groups, small-molecule organic compound functionalization, and polymer modification and composites. Subsequently, an in situ analysis of surface-modified 2D MXenes is presented. This is followed by an overview of the recent progress in the thermal energy management of 2D MXenes and their composites, such as Joule heating, heat dissipation, thermoelectric energy conversion, and photothermal conversion. Finally, some challenges facing the application of 2D MXenes are discussed, and an outlook on surface-modified 2D MXenes is provided.

Construction of two-dimensional bimetal (Fe-Ti) oxide/carbon/MXene architecture from titanium carbide MXene for ultrahigh-rate lithium-ion storage.

The development of battery systems with high specific capacity and power density could fuel various energy-related applications from personal electronics to grid storage. (Fe2.5Ti0.5)1.04O4 possessing high theoretical specific capacity has been considered as a promising high rate anode material for lithium ion batteries due to the replacement of Fe3+ (0.64 Å) by Ti4+ (0.68 Å) with a larger radius to expand the interlayer space for ion intercalation. However, its extreme volume variation upon cycling as well as poor electrical conductivity hinder its further application. To tackle the above problems, in this work, we successfully synthesized two-dimensional (2D) (Fe2.5Ti0.5)1.04O4/C/MXene architecture derived from Ti3C2Tx MXene via solvo-hydrothermal, ultrasound hybridizing and high temperature annealing processes. The (Fe2.5Ti0.5)1.04O4/C/MXene shows a high discharge capacity of 757.2 mAh g-1 after 800 cycles at a current density of 3 A g-1 with excellent rate performance. The superior electrochemical performances are triggered primarily by the incorporation of carbon and MXene into (Fe2.5Ti0.5)1.04O4 moiety to construct a 2D layered structure, which can improve the ion diffusion and electron transport. In addition, the synergistic contributions from diffusion controlled and capacitive processes for (Fe2.5Ti0.5)1.04O4/C/MXene improve the ion diffusion rate and offer high specific capacity at high current density. The MXene-derived synthesis strategy in this work should be a promising pathway to synthesize other anode materials with 2D layered architecture for high performance lithium storage.

A Quasi-Solid-State Tristate Reversible Electrochemical Mirror Device with Enhanced Stability.

Reversible electrochemical mirror (REM) electrochromic devices with electrochemical tunability in multiple optical states are exciting alternatives to conventional electrochromic smart windows. Electrochromic devices are studied extensively, yet widespread adoptions have not been achieved due to problems associated with durability, switching speed, limited options on optical states, and cost. In this study, a REM electrochromic device based on CuSn alloy is developed, which offers highly reversible switching between transparent, greyish-blue, and mirror states via reversible electrodeposition and dissolution. The alloying element, Sn acts as an electrochemical mediator, which facilitates the electrodeposition and dissolution of Cu. The CuSn-based REM device shows superior cycling stability for 2400 cycles (transmittance mode) and 1000 cycles (reflectance mode). The electrodeposited CuSn alloy film is resistant to surface oxidation in ambient air, with a 2.9% difference in reflectance at 2000 nm after 3 days. In addition, the alloy film exhibits excellent NIR reflectance property with thermal modulation of 18.5 °C at a high temperature of 180 °C. The REM device with zero power consumption maintains its mirror state for at least 100 min, making it a promising candidate for energy-efficient applications.

Influence of halide ions on the structure and properties of copper indium sulphide quantum dots.

In the synthesis of CuInS2 quantum dots (QDs), the halide ions present in the copper salts influence the QD growth and optical properties. X-ray absorption spectroscopy allowed rationalizing the halide incorporation in the lattice and the dependence of electronic properties of the material on the ion's polarizability and interaction with hydrophobic moieties.

WS2 Nano-petals and Nano-bristles Supported on Carbon Nanotubes for Electron Emission Applications.

Atomically thin WS2 nano-petals and nano-bristles were synthesized on vertically aligned carbon nanotubes (CNT) via magnetron sputtering at room temperature. The formation of the nano-petal morphology requires reaching a critical threshold in sputter deposition time, below which an amorphous film of WO3 is obtained instead. Increasing the deposition time past a second threshold results in a change to the nano-bristle morphology. Both WS2 nano-petals and nano-bristles were able to significantly enhance the electron emission of properties. The lowest turn-on voltage measured was to be 295 V and 355 V for the nano-petals and nano-bristles respectively, versus 425 V for pristine CNTs. The variation in the turn-on voltage is due to the electrical contacts at the interface between the different WS2 structures, which induces current saturation at high emission currents. These results demonstrate that 2D WS2 layers can be synthesized without the need for chemical routes and high growth temperatures if an appropriate template is employed.

Ferromagnet/Two-Dimensional Semiconducting Transition-Metal Dichalcogenide Interface with Perpendicular Magnetic Anisotropy.

Ferromagnet/two-dimensional transition-metal dichalcogenide (FM/2D TMD) interfaces provide attractive opportunities to push magnetic information storage to the atomically thin limit. Existing work has focused on FMs contacted with mechanically exfoliated or chemically vapor-deposition-grown TMDs, where clean interfaces cannot be guaranteed. Here, we report a reliable way to achieve contamination-free interfaces between ferromagnetic CoFeB and molecular-beam epitaxial MoSe2. We show a spin reorientation arising from the interface, leading to a perpendicular magnetic anisotropy (PMA), and reveal the CoFeB/2D MoSe2 interface allowing for the PMA development in a broader CoFeB thickness-range than common systems such as CoFeB/MgO. Using X-ray magnetic circular dichroism analysis, we attribute generation of this PMA to interfacial d-d hybridization and deduce a general rule to enhance its magnitude. We also demonstrate favorable magnetic softness and considerable magnetic moment preserved at the interface and theoretically predict the interfacial band matching for spin filtering. Our work highlights the CoFeB/2D MoSe2 interface as a promising platform for examination of TMD-based spintronic applications and might stimulate further development with other combinations of FM/2D TMD interfaces.

Temperature-Controlled Vapor Deposition of Highly Conductive p-Type Reduced Molybdenum Oxides by Hydrogen Reduction.

Reduced molybdenum oxide, generally MoO3- x, becomes increasingly metallic as the oxygen level decreases during the reduction of MoO3 to MoO2. Its interesting properties have recently intrigued research on MoO3- x in electrical and electrochemical areas. Lacking effective tools to control the oxygen level is one of the research difficulties for MoO3- x. Herein, we report facile temperature-controlled synthesis of triangular MoO2 and square Mo4O11. The triangular and square flakes showed metallic behavior with conductivity as high as ∼940 and ∼28 S/cm in DC measurement, respectively. The decrease in oxygen level from Mo4O11 to MoO2 affected the density of states mapped in Mo 4d orbitals, leading to higher conductivity for triangular MoO2. Further Mott-Schottky analysis on MoO3- x regrown on carbon fiber paper (CFP) revealed hole mobility of 105-108 cm2 V-1 s-1. The hole carriers at high frequencies are attributed to potential oxygen acceptors, and molybdenum vacancies resulted from limited reduction power of hydrogen.

Toward High-Performance and Low-Cost Hydrogen Evolution Reaction Electrocatalysts: Nanostructuring Cobalt Phosphide (CoP) Particles on Carbon Fiber Paper.

In this communication, we facily fabricated nanostructured CoP particles (150 to 200 nm) on carbon fiber paper (CFP) for hydrogen evolution reaction (HER) by a simple two-step process via a green route. In the first step, crystalline Co3O4 nanocubes (150-200 nm) were loaded on CFP through a hydrothermal process at low temperature (120 °C). Interestingly, crystalline Co3O4 nanocubes with a size 150-200 nm exhibited different growth mechanisms in contrast to the crystalline Co3O4 nanocubes with a size <100 nm reported earlier. In the second step, these crystalline Co3O4 nanocubes were converted to catalytically active CoP particles through chemical vapor deposition (CVD) phosphorization (denoted as CoP/CFP-H). Remarkably, CoP/CFP-H exhibited a low Tafel slope of 49.7 mV/dec and only required overpotentials of 128.1, 144.4, and 190.8 mV to drive geometric current densities of -10, -20, and -100 mA cm-2, respectively. Besides, the CoP/CFP-H also demonstrated an excellent durability in an acidic environment under 2000 sweeps at a high scan rate (100 mV s-1) and a 24 h chronopotentiometry testing. For comparison, CoP was also fabricated through the electrodeposition method, followed by CVD phosphorization (denoted as CoP/CFP-E). It was found that the latter had exhibited inferior activity compared to CoP/CFP-H. The good performances of CoP/CFP-H are essentially due to the rational designs of electrode: (i) the applications of highly HER active CoP electrocatalyst, (ii) the intimate contact of nanostructured CoP on carbon fibers, and (iii) the large electrochemical surface area at electrocatalyst/electrolyte interface due to the large retaining of particles features after phosphorization. Notably, the intermediate Co3O4/CFP can serve as a platform to develop other cobalt-based functional materials.

Synthesizing 2D MoS2 Nanofins on carbon nanospheres as catalyst support for Proton Exchange Membrane Fuel Cells.

Highly dense 2D MoS2 fin-like nanostructures on carbon nanospheres were fabricated and formed the main catalyst support structure in the oxygen reduction reaction (ORR) for polymer electrolyte membrane (PEM) fuel cells. These nanofins were observed growing perpendicular to the carbon nanosphere surface in random orientations and high resolution transmission electron microscope confirmed 2D layers. The PEM fuel cell test showed enhanced electrochemical activity with good stability, generating over 8.5 W.mgPt(-1) as compared to standard carbon black of 7.4 W.mgPt(-1) under normal operating conditions. Electrochemical Impedance Spectroscopy confirmed that the performance improvement is highly due to the excellent water management of the MoS2 lamellar network, which facilitates water retention at low current density and flood prevention at high current density. Reliability test further demonstrated that these nanofins are highly stable in the electrochemical reaction and is an excellent ORR catalyst support.

Amorphous Molybdenum Sulfide on Graphene-Carbon Nanotube Hybrids as Highly Active Hydrogen Evolution Reaction Catalysts.

In this study, we report on the deposition of amorphous molybdenum sulfide (MoSx, with x ≈ 3) on a high specific surface area conductive support of Graphene-Carbon Nanotube hybrids (GCNT) as the Hydrogen Evolution Reaction (HER) catalysts. We found that the high surface area GCNT electrode could support the deposition of MoSx at much higher loadings compared with simple porous carbon paper or flat graphite paper. The morphological study showed that MoSx was successfully deposited on and was in good contact with the GCNT support. Other physical characterization techniques suggested the amorphous nature of the deposited MoSx. With a typical catalyst loading of 3 mg cm(-2), an overpotential of 141 mV was required to obtain a current density of 10 mA cm(-2). A Tafel slope of 41 mV decade(-1) was demonstrated. Both measures placed the MoSx-deposited GCNT electrode among the best performing molybdenum sulfide-based HER catalysts reported to date. The electrode showed a good stability with only a 25 mV increase in overpotential required for a current density of 10 mA cm(-2), after undergoing 500 potential sweeps with vigorous bubbling present. The current density obtained at -0.5 V vs SHE (Standard Hydrogen Electrode potential) decreased less than 10% after the stability test. The deposition of MoSx on high specific surface area conductive electrodes demonstrated to be an efficient method to maximize the catalytic performance toward HER.

One-step Synthesis of Few-layer WS2 by Pulsed Laser Deposition.

Atomically thin tungsten disulfide (WS2) has attracted much attention in recent years due its indirect-to-direct band gap transition, band gap tunability, and giant spin splitting. However, the fabrication of atomically thin WS2 remains largely underdeveloped in comparison to its structural analogue MoS2. Here we report the direct fabrication of highly crystalline few-layer WS2 on silver substrates by pulse laser deposition at the relatively low temperature of 450 °C. The growth takes places by conventional epitaxy, through the in-situ formation of nearly lattice-matching Ag2S on the silver surface. Intriguingly, it was observed that the resulting film was composed of not only the usual semiconducting 2H-WS2 structure but also the less common metallic 1T-WS2. Modifications of the synthesis parameters allow for control over the crystalline quality, film thickness and crystal phase composition of the resulting WS2 film.

Novel nitrogen doped graphene sponge with ultrahigh capacitive deionization performance.

As water shortage has become a serious global problem, capacitive deionization (CDI) with high energy efficiency and low cost, is considered as a promising desalination technique to solve this problem. To date, CDI electrodes are mainly made up of porous carbon materials. However, the electrosorption performance obtained by now still cannot meet the demand of practical application. Therefore, a rationally designed structure of electrode materials has been an urgent need for CDI application. Here, a novel nitrogen-doped graphene sponge (NGS), with high specific surface area and rationally designed structure was fabricated, and used as CDI electrodes for the first time. The results show that NGS exhibits an ultrahigh electrosorption capacity of 21.0 mg g(-1) in ∼ 500 mg L(-1) NaCl solution, and to our knowledge, it is the highest value reported for carbon electrodes in similar experimental conditions by now. NGS in this work is expected to be a promising candidate as CDI electrode material.

Facile synthesis of novel graphene sponge for high performance capacitive deionization.

Capacitive deionization (CDI) is an effective desalination technique offering an appropriate route to obtain clean water. In order to obtain excellent CDI performance, a rationally designed structure of electrode materials has been an urgent need for CDI application. In this work, a novel graphene sponge (GS) was proposed as CDI electrode for the first time. The GS was fabricated via directly freeze-drying graphene oxide solution followed by annealing in nitrogen atmosphere. The morphology, structure and electrochemical performance of GS were characterized by scanning electron microscopy, Raman spectroscopy, nitrogen adsorption-desorption, X-ray photoelectron spectroscopy, cyclic voltammetry and electrochemical impedance spectroscopy. The electrosorption performance of GS in NaCl solution was studied and compared with pristine graphene (PG). The results show that due to the unique 3D interconnected porous structure, large accessible surface area and low charge transfer resistance, GS electrode exhibits an ultrahigh electrosorption capacity of 14.9 mg g(-1) when the initial NaCl concentration is ~500 mg L(-1), which is about 3.2 times of that of PG (4.64 mg g(-1)), and to our knowledge, it should be the highest value reported for graphene electrodes in similar experimental conditions by now. These results indicate that GS should be a promising candidate for CDI electrode.

Enhanced electrocatalytic activity of MoS(x) on TCNQ-treated electrode for hydrogen evolution reaction.

Molybdenum sulfide has recently attracted much attention because of its low cost and excellent catalytical effects in the application of hydrogen evolution reaction (HER). To improve the HER efficiency, many researchers have extensively explored various avenues such as material modification, forming hybrid structures or modifying geometric morphology. In this work, we reported a significant enhancement in the electrocatalytic activity of the MoSx via growing on Tetracyanoquinodimethane (TCNQ) treated carbon cloth, where the MoSx was synthesized by thermolysis from the ammonium tetrathiomolybdate ((NH4)2MoS4) precursor at 170 °C. The pyridinic N- and graphitic N-like species on the surface of carbon cloth arising from the TCNQ treatment facilitate the formation of Mo(5+) and S2(2-) species in the MoSx, especially with S2(2-) serving as an active site for HER. In addition, the smaller particle size of the MoSx grown on TCNQ-treated carbon cloth reveals a high ratio of edge sites relative to basal plane sites, indicating the richer effective reaction sites and superior electrocatalytic characteristics. Hence, we reported a high hydrogen evolution rate for MoSx on TCNQ-treated carbon cloth of 6408 mL g(-1) cm(-2) h(-1) (286 mmol g(-1) cm(-2) h(-1)) at an overpotential of V = 0.2 V. This study provides the fundamental concepts useful in the design and preparation of transition metal dichalcogenide catalysts, beneficial in the development in clean energy.

Growth mechanism of pulsed laser fabricated few-layer MoS2 on metal substrates.

Pulsed laser deposition (PLD) on metal substrates has recently been discovered to present an alternative method for producing highly crystalline few-layer MoS2. However, not every metal behaves in the same manner during film growth, and hence, it is crucial that the ability of various metals to produce crystalline MoS2 be thoroughly investigated. In this work, MoS2 was deposited on metal substrates, Al, Ag, Ni, and Cu, using a pulsed laser. Highly crystalline few-layer MoS2 was successfully grown on Ag, but is absent in Al, Ni, and Cu under specific growth conditions. This discrepancy was attributed to either excessively strong or insufficient adlayer-substrate interactions. In the case of Al, the effects of the strong interface interactions can be offset by increasing the amount of source atoms supplied, thereby producing semicrystalline few-layer MoS2. The results show that despite PLD being a physical vapor deposition technique, both physical and chemical processes play an important role in MoS2 growth on metal substrates.

Development of an amorphous selenium-based photodetector driven by a diamond cold cathode.

Amorphous-selenium (a-Se) based photodetectors are promising candidates for imaging devices, due to their high spatial resolution and response speed, as well as extremely high sensitivity enhanced by an internal carrier multiplication. In addition, a-Se is reported to show sensitivity against wide variety of wavelengths, including visible, UV and X-ray, where a-Se based flat-panel X-ray detector was proposed. In order to develop an ultra high-sensitivity photodetector with a wide detectable wavelength range, a photodetector was fabricated using a-Se photoconductor and a nitrogen-doped diamond cold cathode. In the study, a prototype photodetector has been developed, and its response to visible and ultraviolet light are characterized.

Structural studies of aluminium nitride embedded in amorphous carbon.

Aluminum nitride containing diamond-like carbon was fabricated with pulsed laser deposition without post processing. The compositions of the targets used were varied at 1, 5, 10, 15 at.% and pure carbon was used as a reference. The films were comprehensively characterized with Atomic force microscope (AFM), X-ray photoelectron spectroscopy (XPS) and Transmission electron microscopy (TEM). Roughness analysis using AFM showed an increasing root-mean-square (RMS) roughness with increasing AIN content in target, while XPS analysis showed that the aluminum-nitrogen bonding was still present in the films after the fabrication process. Microstructural studies and selected area electron diffraction (SAED) pattern confirmed the presence of AIN crystals in DLC matrix. This nanostructured composite material is useful for luminescence applications.

Electrical performance of low cost cathodes prepared by plasma sputtering deposition in microbial fuel cells.

Microbial fuel cells (MFCs) could potentially be utilized for a variety of applications in the future from biosensors to wastewater treatment. However, the amount of costly platinum (Pt) used as a catalyst should be minimized via innovative deposition methods such as sputtering. In addition, alternative and low-cost catalysts, such as cobalt (Co), should be sought. In this study, ultra low Pt or Co cathodes (0.1 mg cm(-2)) were manufactured by plasma sputtering deposition and scanning electron micrographs revealed nano-clusters of metal catalyst in a porous structure favorable to the three-phase heterogeneous catalytic reaction. When operated in single-chamber air-cathode MFCs, sputtered-Co cathodes generated on average the same power as sputtered-Pt cathodes (0.27 mW cell(-1)) and only 27% less than conventional Pt-ink cathodes with a catalyst load 5 times higher (0.5 mg cm(-2)). Finally, microscopy and molecular analyses showed evidence of biocatalysis activity on metal-free cathodes.

Bonelike apatite formation utilizing carbon nanotubes as template.

Template-induced hydroxyapatite (HA) has broad prospects in the applied fields of regenerative medicine and bone repair. HA thin coatings have been deposited on vertically aligned multiwalled carbon nanotubes (CNTs) via the high-temperature radio-frequency (rf) magnetron sputtering deposition technique. Simulated body fluid (SBF) solution has been used to soak and incubate the HA/CNTs nanocomposites at 37 degrees C. SEM, EDS, XRD, and FTIR characterizations revealed bonelike apatite formation on top of HA/CNTs composites. Coating HA material on well-aligned CNT-template provides a way of combining the superior mechanical properties and chemical stability of the CNTs with the excellent biochemical properties of HA.