Mark A. Bissett

Characterization of MoS2–Graphene Composites for High-Performance Coin Cell Supercapacitors

Two-dimensional materials, such as graphene and molybdenum disulfide (MoS2), can greatly increase the performance of electrochemical energy storage devices because of the combination of high surface area and electrical conductivity. Here, we have investigated the performance of solution exfoliated MoS2 thin flexible membranes as supercapacitor electrodes in a symmetrical coin cell arrangement using an aqueous electrolyte (Na2SO4). By adding highly conductive graphene to form nanocomposite membranes, it was possible to increase the specific capacitance by reducing the resistivity of the electrode and altering the morphology of the membrane. With continued charge/discharge cycles the performance of the membranes was found to increase significantly (up to 800%), because of partial re-exfoliation of the layered material with continued ion intercalation, as well as increasing the specific capacitance through intercalation pseudocapacitance. These results demonstrate a simple and scalable application of layered 2D materials toward electrochemical energy storage.

Enhanced Chemical Reactivity of Graphene Induced by Mechanical Strain

Control over chemical reactivity is essential in the field of nanotechnology. Graphene is a two-dimensional atomic sheet of sp(2) hybridized carbon with exceptional properties that can be altered by chemical functionalization. Here, we transferred single-layer graphene onto a flexible substrate and investigated the functionalization using different aryl diazonium molecules while applying mechanical strain. We found that mechanical strain can alter the structure of graphene, and dramatically increase the reaction rate, by a factor of up to 10, as well as increase the final degree of functionalization. Furthermore, we demonstrate that mechanical strain enables functionalization of graphene for both p- and n-type dopants, where unstrained graphene showed negligible reactivity. Theoretical calculations were also performed to support the experimental findings. Our findings offer a simple approach to control the chemical reactivity of graphene through the application of mechanical strain, allowing for a tuning of the properties of graphene.

Strain engineering the properties of graphene and other two-dimensional crystals

Graphene has been widely studied for its many extraordinary properties, and other two-dimensional layered materials are now gaining increased interest. These excellent properties make thin layer materials very attractive for integration into a wide variety of technologies, particularly in flexible optoelectronic devices. Therefore, gaining control over these properties will allow for a more focused design and optimisation of these possible technologies. Through the application of mechanical strain it is possible to alter the electronic structures of two-dimensional crystals, such as graphene and transition metal dichalcogenides (e.g. MoS2), and these changes in electronic structure can alter their behaviour. In this perspective we discuss recent advances in the strain engineering of thin layer materials, with a focus on using Raman spectroscopy and electrical transport to investigate the effect of strain as well as the effect of strain on the chemical functionalisation of graphene.

Epitaxial growth and electronic properties of large hexagonal graphene domains on Cu(111) thin film

Large hexagonal single-crystalline domains of single-layer graphene are epitaxially grown by ambient-pressure chemical vapor deposition over a thin Cu(111) film deposited on c-plane sapphire. The hexagonal graphene domains with a maximum size of 100 µm are oriented in the same direction due to the epitaxial growth. Reflecting high crystallinity, a clear band structure with the Dirac cone is observed by angle-resolved photoelectron spectroscopy (ARPES), and a high carrier mobility exceeding 4,000 cm2 V-1 s-1 is obtained on SiO2/Si at room temperature. Our epitaxial approach combined with large domain growth is expected to contribute to future electronic applications.

Effect of domain boundaries on the Raman spectra of mechanically strained graphene

We investigate the effect of mechanical strain on graphene synthesized by chemical vapor deposition (CVD) transferred onto flexible polymer substrates by observing the change in the Raman spectrum and then compare this to the behavior of exfoliated graphene. Previous studies into the effect of strain on graphene have focused on mechanically exfoliated graphene, which consists of large single domains. However, for wide scale applications CVD produced films are more applicable, and these differ in morphology, instead consisting of a patchwork of smaller domains separated by domain boundaries. We find that under strain the Raman spectra of CVD graphene transferred onto a silicone elastomer exhibits unusual behavior, with the G and 2D band frequencies decreasing and increasing respectively with applied strain. This unusual Raman behavior is attributed to the presence of domain boundaries in polycrystalline graphene causing unexpected shifts in the electronic structure. This was confirmed by the lack of such behavior in mechanically exfoliated large domain graphene and also in large single-crystal graphene domains grown by CVD. Theoretical calculation of G band for a given large shear strain may explain the unexpected shifts while the shift of the Dirac points from the K point explain the conventional behavior of a 2D band under the strain.

Photoelectrochemistry of Pristine Mono- and Few-Layer MoS2.

Two-dimensional crystals are promising building blocks for the new generation of energy materials due to their low volume, high surface area, and high transparency. Electrochemical behavior of these crystals determines their performance in applications such as energy storage/conversion, sensing, and catalysis. Nevertheless, the electrochemistry of an isolated monolayer of molybdenum disulfide, which is one of the most promising semiconducting crystals, has not been achieved to date. We report here on photoelectrochemical properties of pristine monolayer and few-layer basal plane MoS2, namely the electron transfer kinetics and electric double-layer capacitance, supported by an extensive physical and chemical characterization. This enables a comparative qualitative correlation among the electrochemical data, MoS2 structure, and external illumination, although the absolute magnitudes of the electron transfer and capacitance are specific to the redox mediator and electrolyte used in these measurements ([Ru(NH3)6](3+/2+) and LiCl, respectively). Our work shows a strong dependence of the electrochemical properties on the number of MoS2 layers and illumination intensity and proves that an effective interlayer charge transport occurs in bulk MoS2. This highlights the exciting opportunities for tuning of the electrochemical performance of MoS2 through modification of its structure, external environment, and illumination.

Asymmetric MoS2/Graphene/Metal Sandwiches: Preparation, Characterization, and Application

The polarizable organic/water interface is used to construct MoS2 /graphene nanocomposites, and various asymmetrically dual-decorated graphene sandwiches are synthesized. High-resolution transmission electron microscopy and 3D electron tomography confirm their structure. These dual-decorated graphene-based hybrids show excellent hydrogen evolution activity and promising capacitance performance.

Electron transfer kinetics on natural crystals of MoS2 and graphite

Here, we evaluate the electrochemical performance of sparsely studied natural crystals of molybdenite and graphite, which have increasingly been used for fabrication of next generation monolayer molybdenum disulphide and graphene energy storage devices. Heterogeneous electron transfer kinetics of several redox mediators, including Fe(CN)6(3-/4-), Ru(NH3)6(3+/2+) and IrCl6(2-/3-) are determined using voltammetry in a micro-droplet cell. The kinetics on both materials are studied as a function of surface defectiveness, surface ageing, applied potential and illumination. We find that the basal planes of both natural MoS2 and graphite show significant electroactivity, but a large decrease in electron transfer kinetics is observed on atmosphere-aged surfaces in comparison to in situ freshly cleaved surfaces of both materials. This is attributed to surface oxidation and adsorption of airborne contaminants at the surface exposed to an ambient environment. In contrast to semimetallic graphite, the electrode kinetics on semiconducting MoS2 are strongly dependent on the surface illumination and applied potential. Furthermore, while visibly present defects/cracks do not significantly affect the response of graphite, the kinetics on MoS2 systematically accelerate with small increase in disorder. These findings have direct implications for use of MoS2 and graphene/graphite as electrode materials in electrochemistry-related applications.

Increased chemical reactivity achieved by asymmetrical ‘Janus’ functionalisation of graphene

Chemical functionalisation is a promising method to tune the electronic structure of graphene, and the two-dimensional structure of graphene enables access to both of its faces for various types of functionalisation. Here, we present the effect of covalent functionalisation on the Raman spectrum in terms of monofacial (one-sided) and bifacial (two-sided) functionalisation using both monolayer and bilayer graphene. Asymmetrical or ‘Janus’ functionalisation is found to provide significantly increased levels of doping compared to other schemes allowing for control over graphenes electronic structure as well as control over surface functionality.

Facile fabrication of metal–organic framework HKUST-1-based rewritable data storage devices

Metal–organic framework (MOF) HKUST-1 coated Cu electrodes synthesised by a quick and scalable anodic dissolution process and assembled into a sealed, symmetrical, two electrode coin cell configuration are shown to demonstrate redox-based data storage behaviour. The observed behaviour is confirmed to be definitively due to the HKUST-1 itself as opposed to the underlying Cu/CuO electrode surface by demonstration of the same effect using HKUST-1/PVDF composite coated carbon fibre electrodes. This data storage behaviour is attributed to the immobilisation of a fixed number of electrically accessible Cu cations within the porous HKUST-1 framework that are in the vicinity of the electrode surfaces and their ability to undergo facile Cu2+/+ redox interconversion as a function of the potential applied across the electrodes. This proposed redox-based mechanism for the observed data storage effect has never previously been reported for MOF-based devices. Optimisation of electrolyte composition, electrolyte concentration and electrode separation results in “on”/”off” current densities of the order of 1 mA cm−2, an “on” : “off” ratio of ∼5, “on”/”off” states stable to at least 10 consecutive reads, rewritability that persists over 6000 cycles, and the storage of data that can still be read hours after writing. The resulting data storage devices are more stable to successive reading and can be rewritten many more times than other previously reported pure MOF-based devices.