Synthesis of 2D anatase TiO2 with highly reactive facets by fluorine-free topochemical conversion of 1T-TiS2 nanosheets.

Two-dimensional (2D) anatase titanium dioxide (TiO2) is expected to exhibit different properties as compared to anatase nanocrystallites, due to its highly reactive exposed facets. However, access to 2D anatase TiO2 is limited by the non-layered nature of the bulk crystal, which does not allow use of top-down chemical exfoliation. Large efforts have been dedicated to the growth of 2D anatase TiO2 with high reactive facets by bottom-up approaches, which relies on the use of harmful chemical reagents. Here, we demonstrate a novel fluorine-free strategy based on topochemical conversion of 2D 1T-TiS2 for the production of single crystalline 2D anatase TiO2, exposing the {001} facet on the top and bottom and {100} at the sides of the nanosheet. The exposure of these faces, with no additional defects or doping, gives rise to a significant activity enhancement in the hydrogen evolution reaction, as compared to commercially available Degussa P25 TiO2 nanoparticles. Because of the strong potential of TiO2 in many energy-based applications, our topochemical approach offers a low cost, green and mass scalable route for production of highly crystalline anatase TiO2 with well controlled and highly reactive exposed facets.

All-2D Material Inkjet-Printed Capacitors: Toward Fully Printed Integrated Circuits.

A well-defined insulating layer is of primary importance in the fabrication of passive ( e.g., capacitors) and active ( e.g., transistors) components in integrated circuits. One of the most widely known two-dimensional (2D) dielectric materials is hexagonal boron nitride (hBN). Solution-based techniques are cost-effective and allow simple methods to be used for device fabrication. In particular, inkjet printing is a low-cost, noncontact approach, which also allows for device design flexibility, produces no material wastage, and offers compatibility with almost any surface of interest, including flexible substrates. In this work, we use water-based and biocompatible graphene and hBN inks to fabricate all-2D material and inkjet-printed capacitors. We demonstrate an areal capacitance of 2.0 ± 0.3 nF cm-2 for a dielectric thickness of ∼3 µm and negligible leakage currents, averaged across more than 100 devices. This gives rise to a derived dielectric constant of 6.1 ± 1.7. The inkjet printed hBN dielectric has a breakdown field of 1.9 ± 0.3 MV cm-1. Fully printed capacitors with sub-micrometer hBN layer thicknesses have also been demonstrated. The capacitors are then exploited in two fully printed demonstrators: a resistor-capacitor (RC) low-pass filter and a graphene-based field effect transistor.

Chelant Enhanced Solution Processing for Wafer Scale Synthesis of Transition Metal Dichalcogenide Thin Films.

It is of paramount importance to improve the control over large area growth of high quality molybdenum disulfide (MoS2) and other types of 2D dichalcogenides. Such atomically thin materials have great potential for use in electronics, and are thought to make possible the first real applications of spintronics. Here in, a facile and reproducible method of producing wafer scale atomically thin MoS2 layers has been developed using the incorporation of a chelating agent in a common organic solvent, dimethyl sulfoxide (DMSO). Previously, solution processing of a MoS2 precursor, ammonium tetrathiomolybdate ((NH4)2MoS4), and subsequent thermolysis was used to produce large area MoS2 layers. Our work here shows that the use of ethylenediaminetetraacetic acid (EDTA) in DMSO exerts superior control over wafer coverage and film thickness, and the results demonstrate that the chelating action and dispersing effect of EDTA is critical in growing uniform films. Raman spectroscopy, photoluminescence (PL), x-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM) and high-resolution scanning transmission electron microscopy (HR-STEM) indicate the formation of homogenous few layer MoS2 films at the wafer scale, resulting from the novel chelant-in-solution method.

Carbon-Coated, Diatomite-Derived Nanosilicon as a High Rate Capable Li-ion Battery Anode.

Silicon is produced in a variety of ways as an ultra-high capacity lithium-ion battery (LIB) anode material. The traditional carbothermic reduction process required is expensive and energy-intensive; in this work, we use an efficient magnesiothermic reduction to convert the silica-based frustules within diatomaceous earth (diatomite, DE) to nanosilicon (nanoSi) for use as LIB anodes. Polyacrylic acid (PAA) was used as a binder for the DE-based nanoSi anodes for the first time, being attributed for the high silicon utilization under high current densities (up to 4C). The resulting nanoSi exhibited a high BET specific surface area of 162.6 cm2 g-1, compared to a value of 7.3 cm2 g-1 for the original DE. DE contains SiO2 architectures that make ideal bio-derived templates for nanoscaled silicon. The DE-based nanoSi anodes exhibit good cyclability, with a specific discharge capacity of 1102.1 mAh g-1 after 50 cycles at a C-rate of C/5 (0.7 A gSi-1) and high areal loading (2 mg cm-2). This work also demonstrates the fist rate capability testing for a DE-based Si anode; C-rates of C/30 - 4C were tested. At 4C (14.3 A gSi-1), the anode maintained a specific capacity of 654.3 mAh g-1 - nearly 2x higher than graphite's theoretical value (372 mAh g-1).

Bio-Derived, Binderless, Hierarchically Porous Carbon Anodes for Li-ion Batteries.

Here we explore the electrochemical performance of pyrolyzed skins from the species A. bisporus, also known as the Portobello mushroom, as free-standing, binder-free, and current collector-free Li-ion battery anodes. At temperatures above 900 °C, the biomass-derived carbon nanoribbon-like architectures undergo unique processes to become hierarchically porous. During heat-treatment, the oxygen and heteroatom-rich organics and potassium compounds naturally present in the mushroom skins play a mutual role in creating inner void spaces throughout the resulting carbon nanoribbons, which is a process analogous to KOH-activation of carbon materials seen in literature. The pores formed in the pyrolytic carbon nanoribbons range in size from sub-nanometer to tens of nanometers, making the nanoribbons micro, meso, and macroporous. Detailed studies were conducted on the carbon nanoribbons using SEM and TEM to study morphology, as well as XRD and EDS to study composition. The self-supporting nanoribbon anodes demonstrate significant capacity increase as they undergo additional charge/discharge cycles. After a pyrolysis temperature of 1100 °C, the pristine anodes achieve over 260 mAh/g after 700 cycles and a Coulombic efficiency of 101.1%, without the use of harmful solvents or chemical activation agents.

Two step growth phenomena of molybdenum disulfide-tungsten disulfide heterostructures.

Here, we report the first demonstration of atomically thin vertically stacked MoS2/WS2 heterostructures, achieved via a two-step chemical vapour deposition (CVD) growth process. Highly ordered stacking of heterostructure domains and patterned defects have been observed. Computations based on first principles have been performed to understand observed enhanced photoluminescence of the heterostructure.

Monodisperse porous silicon spheres as anode materials for lithium ion batteries.

Highly monodisperse porous silicon nanospheres (MPSSs) are synthesized via a simple and scalable hydrolysis process with subsequent surface-protected magnesiothermic reduction. The spherical nature of the MPSSs allows for a homogenous stress-strain distribution within the structure during lithiation and delithiation, which dramatically improves the electrochemical stability. To fully extract the real performance of the MPSSs, carbon nanotubes (CNTs) were added to enhance the electronic conductivity within the composite electrode structure, which has been verified to be an effective way to improve the rate and cycling performance of anodes based on nano-Si. The Li-ion battery (LIB) anodes based on MPSSs demonstrate a high reversible capacity of 3105 mAh g(-1). In particular, reversible Li storage capacities above 1500 mAh g(-1) were maintained after 500 cycles at a high rate of C/2. We believe this innovative approach for synthesizing porous Si-based LIB anode materials by using surface-protected magnesiothermic reduction can be readily applied to other types of SiOx nano/microstructures.

Towards scalable binderless electrodes: carbon coated silicon nanofiber paper via Mg reduction of electrospun SiO2 nanofibers.

The need for more energy dense and scalable Li-ion battery electrodes has become increasingly pressing with the ushering in of more powerful portable electronics and electric vehicles (EVs) requiring substantially longer range capabilities. Herein, we report on the first synthesis of nano-silicon paper electrodes synthesized via magnesiothermic reduction of electrospun SiO2 nanofiber paper produced by an in situ acid catalyzed polymerization of tetraethyl orthosilicate (TEOS) in-flight. Free-standing carbon-coated Si nanofiber binderless electrodes produce a capacity of 802 mAh g(-1) after 659 cycles with a Coulombic efficiency of 99.9%, which outperforms conventionally used slurry-prepared graphite anodes by over two times on an active material basis. Silicon nanofiber paper anodes offer a completely binder-free and Cu current collector-free approach to electrode fabrication with a silicon weight percent in excess of 80%. The absence of conductive powder additives, metallic current collectors, and polymer binders in addition to the high weight percent silicon all contribute to significantly increasing capacity at the cell level.

SiO2-coated sulfur particles with mildly reduced graphene oxide as a cathode material for lithium-sulfur batteries.

For the first time, SiO2-coated sulfur particles (SCSPs) were fabricated via a facile two-step wet chemical process for application as a novel lithium-sulfur cathode material. With the addition of mildly reduced graphene oxide (mrGO), SCSPs demonstrate even greater cycling stability, maintaining over 700 mA h g(-1) after the 50(th) cycle.

Oxygen etching of thick MoS2 films.

Oxygen annealing of thick MoS2 films results in randomly oriented and controllable triangular etched shapes, forming pits with uniform etching angles. These etching morphologies differ across the sample based on the defect sites situated on the basal plane surface, forming numerous features in different bulk sample thicknesses.