Lithium-sulfur (Li-S) chemistry is projected to be one of the most promising for next-generation battery technology, and controlling the inherent "polysulfide shuttle" process has become a key research topic in the field. Regulating intermediary polysulfide dissolution by understanding the metamorphosis is essential for realizing stable and high-energy-density Li-S batteries. As of yet, a clear consensus on the basic surface/interfacial properties of the sulfur electrode has not been achieved, although the catalytic phenomenon has been shown to result in enhanced cell stability. Herein, we present evidence that the polysulfide shuttle in a Li-S battery can be stabilized by using electrocatalytic transition metal dichalcogenides (TMDs). Physicochemical transformations at the electrode/electrolyte interface of atomically thin monolayer/few-layer TMDs were elucidated using a combination of spectroscopic and microscopic analysis techniques. Preferential adsorption of higher order liquid polysulfides and subsequent conversion to lower order solid species in the form of dendrite-like structures on the edge sites of TMDs have been demonstrated. Further, detailed electrochemical properties such as activation energy, exchange current density, rate capabilities, cycle life, etc. have been investigated by synthesizing catalytically active nanostructured TMDs in bulk quantity using a liquid-based shear-exfoliation method. Unveiling a specific capacity of 590 mAh g at 0.5 C rate and stability over 350 cycles clearly indicates yet another promising application of two-dimensional TMDs.
Monolayer transition metal dichalcogenides (TMD) have numerous potential applications in ultrathin electronics and photonics. The exposure of TMD-based devices to light generates photo-carriers resulting in an enhanced conductivity, which can be effectively used, e.g., in photodetectors. If the photo-enhanced conductivity persists after removal of the irradiation, the effect is known as persistent photoconductivity (PPC). Here we show that ultraviolet light (λ = 365 nm) exposure induces an extremely long-living giant PPC (GPPC) in monolayer MoS2 (ML-MoS2) field-effect transistors (FET) with a time constant of ~30 days. Furthermore, this effect leads to a large enhancement of the conductivity up to a factor of 107. In contrast to previous studies in which the origin of the PPC was attributed to extrinsic reasons such as trapped charges in the substrate or adsorbates, we show that the GPPC arises mainly from the intrinsic properties of ML-MoS2 such as lattice defects that induce a large number of localized states in the forbidden gap. This finding is supported by a detailed experimental and theoretical study of the electric transport in TMD based FETs as well as by characterization of ML-MoS2 with scanning tunneling spectroscopy, high-resolution transmission electron microscopy, and photoluminescence measurements. The obtained results provide a basis for the defect-based engineering of the electronic and optical properties of TMDs for device applications.
Conducting polymer actuators such as polypyrrole (PPy) microactuators are interesting candidates to drive autonomous microrobotic devices that require low weight and low power. Simple PPy tri-layer bending type microactuators that operate in air have been demonstrated previously but they lack individual control and had problems with short circuiting due to electrical connections. The lack of micropatterning methods and proper interfacing are currently major obstacles in the development of PPy tri-layer microactuators. Here, we report for the first time methods for successfully patterning and interfacing of such tri-layer PPy microactuators. The PPy tri-layer actuators were patterned using adapted microfabrication technology including photolithography. The interface was based on a flexible printed circuit board comprising the electronic circuit into which the actuator unit was embedded. It showed that the microfabricated tri-layer actuators functioned as good as the normally fabricated actuators. The new interface seemed to actually improve the actuator performance. This interfacing method could also be applied to other electroactive polymer devices, such as ion polymer metal composites (IPMC) and dielectric elastomers (DE).
Due to its unique electronic band characteristics (presence of d-orbital in both Mo and Se atoms), MoSe has potential to exhibit high electrical conductivity and superior hydrogen evolution reaction (HER) kinetics when compared to other transition-metal dichalcogenides. Though various strategies were employed earlier to obtain MoSe structure with different shapes and morphologies, precise control on achieving both Mo- and Se-edge sites and understanding their interaction with reactants in HER remains to be challenging. Here, we successfully demonstrate the vapor diffusion method to grow highly crystalline MoSe nanoflowers on carbon cloth in a vertical orientation. Uniformly dispersed nanoflowers with Mo- and Se-edge sites exhibited remarkable electrocatalytic activity on hydrogen reduction in terms of low Tafel slope and high exchange current density. The existence of a strong interaction between MoSe and carbon cloth assists in long-term hydrogen production and confirms the exceptional durability of the catalyst. A comprehensive evidence for hydrogen adsorption on dual active sites, viz., Mo- and Se-edges of MoSe, is provided using X-ray photoelectron spectroscopy and in situ Raman spectroscopy containing a specially designed liquid immersion objective lens.
We present a novel methodology to synthesize two-dimensional (2D) lateral heterostructures of graphene and MoS2 sheets with molecular carbon nanomembranes (CNMs), which is based on electron beam induced stitching. Monolayers of graphene and MoS2 were grown by chemical vapor deposition (CVD) on copper and SiO2 substrates, respectively, transferred onto gold/mica substrates and patterned by electron beam lithography or photolithography. Self-assembled monolayers (SAMs) of aromatic thiols were grown on the gold film in the areas where the 2D materials were not present. An irradiation with a low energy electron beam was employed to convert the SAMs into CNMs and simultaneously stitching the CNM edges to the edges of graphene and MoS2, therewith forming a heterogeneous but continuous film composed of two different materials. The formed lateral heterostructures possess a high mechanical stability, enabling their transfer from the gold substrate onto target substrates and even the preparation as freestanding sheets. We characterized the individual steps of this synthesis and the structure of the final heterostructures by complementary analytical techniques including optical microscopy, Raman spectroscopy, atomic force microscopy (AFM), helium ion microscopy (HIM), X-ray photoelectron spectroscopy (XPS) and high-resolution transmission electron microscopy (HRTEM) and find that they possess nearly atomically sharp boundaries.
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