Stacked Graphene Research Articles

Nonperturbative theory of effective Hamiltonians for deformations in two-dimensional materials: Moiré systems and dislocations

We provide a method for the generation of effective continuum Hamiltonians that goes beyond the well known k.p method in being equally effective in both high, and low (or no) symmetry situations. Our approach is based on a surprising exact map of the two-centre tight-binding method onto a compact continuum Hamiltonian, with a precise condition given for the hermiticity of the latter object. We apply this method to a broad range of low dimensional systems of both high and low symmetry: graphene, graphdiyne, {\gamma}-graphyne, 6,6,12-graphyne, twist bilayer graphene, and partial dislocation networks in Bernal stacked bilayer graphene. For the single layer systems the method yields Hamiltonians for the ideal lattices, as well as a systematic theory for corrections due to deformation. In the case of bilayer graphene we provide a compact expression for an effective field capable of describing any stacking deformation of the bilayer; twist bilayer graphene, as well as the partial dislocation network in AB stacked graphene, emerge as special cases of this field. For the latter system we find (i) charge pooling on the mosaic of AB and AC segments near the Dirac point and (ii) localized current carrying states on the partials with the current density characterized by both intralayer and interlayer components.

Evaluation of the mechanical properties of carbon fiber/polymer resin interfaces by molecular simulation

Herein, we evaluate the mechanical properties of carbon fiber/polymer interfaces using three types of specimens: carbon fiber/vinyl ester resin, carbon fiber/epoxy resin, and carbon fiber/polyimide resin. Microbonding tests were performed and the fiber load at interfacial debonding was obtained. By performing finite element analysis, the true interfacial strengths were determined. The strength values followed the order: polyimide > epoxy > vinyl ester for the specimens tested. Molecular modeling was also performed for these specimens. Three stacked graphene layers were used to represent the carbon fiber surface and the interfacial energy was determined. The interfacial energy of the three systems followed the same order as the strength values. The molecular simulations allowed for a qualitative discussion of the material properties. In addition, an interfacial debonding simulation was performed, however the resin part failed instead of the interface, indicating that we evaluated the resin strength but not the interfacial strength. For the quantitative evaluation of interfacial debonding strength, further studies are necessary.

In-line chemiresistors based on multilayer graphene for cadmium dication sensing in water

We report that multilayer graphene exfoliated from graphite at sufficiently low point-defect density, and intercalated by poly(ethylene glycol)-block-poly(propylene glycol)-block-poly (ethylene glycol) (PEG-PPG-PEG) block copolymers of appropriate chain length, functions as a sorbent and detector for cadmium dications in water, which remain trapped within the graphene interlayers, thus changing the device’s electrical resistivity. Graphitic samples at different defectiveness – synthetic graphite and high-quality natural graphite – are exfoliated by PEG-PPG-PEG at different chain lengths (Mn ≈ 1100–14,600 amu). The resulting multilayer graphene “cakes” are incorporated into gap-cell chemiresistors assembled onto microporous supports. The resulting devices are nanoporous and can be inserted in-line in water filtration systems. We have monitored their resistivity as a function of the concentration of specific metal dications (Cd2+, Hg2+ and Mn2+) in the water passing through the devices. Although dication concentrations (of the order of a few ppb) are too low to directly affect the solution ionic conductivity, the solid-state resistivity of our graphene-based chemiresistors decreased at increasing Cd2+ concentration, while the effect was less significant for the other types of ions. We attribute this to Cd2+ intercalation within graphene stacks. It appears that Cd2+ possesses the optimal hydrodynamic radius for being trapped within graphene layers intercalated by PEG-PPG-PEG of appropriate chain length, leading to enhanced Cd2+ sensing. Our chemiresistors are of low cost and can be easily computer controlled.

Tunable terahertz structure based on graphene hyperbolic metamaterials

Photoexcited graphene can behave as the gain medium aiming to come up with the coherent radiation at low THz spectral region. However, its response is very weak because of its atomic dimensions. Herein, a different design aiming to obtain effective tunable THz amplifiers, having small dimensions and lasers with broadband operation based on active THz hyperbolic metamaterials (HMM) is demonstrated. HMMs are considered by employing multiple stacked photoexcited graphene sheets divided by dielectric spacers. Herein, we study and characterize the hyperbolic THz regime of the studied atomic active HMM. A broadband slow-wave propagation regime takes place if the graphene-based HMM system is periodically patterned. This occurs due to the hyperbolic dispersion. Doing so, reconfigurable amplification of THz waves in a broad-spectrum region is attained. This might be engineered by tuning the quasi-Fermi level of graphene. Moreover, the mechanisms leading to the increase of the frequency region of bound surface wave have been proposed in the frame of the current study.

Interfacial Engineering of Graphene Nanosheets at MgO Particles for Thermal Conductivity Enhancement of Polymer Composites

An important task in facilitating the development of thermally conducting graphene/polymer nanocomposites is to suppress the intrinsically strong intersheet π-π stacking of graphene, and thereby to improve the exfoliation and dispersion of graphene in the matrix. Here, a pre-programmed intercalation approach to realize the in situ growth of graphene nanosheets at the inorganic template is demonstrated. Specifically, microsized MgO granules with controlled geometrical size were synthesized using a precipitation method, allowing the simultaneous realization of high surface activity. In the presence of a carbon and nitrogen source, the MgO granules were ready to induce the formation of graphene nanosheets (G@MgO), which allowed for the creation of tenacious linkages between graphene and template. More importantly, the incorporation of G@MgO into polymer composites largely pushed up the thermal conductivity, climbing from 0.39 W/m∙K for pristine polyethylene to 8.64 W/m∙K for polyethylene/G@MgO (60/40). This was accompanied by the simultaneous promotion of mechanical properties (tensile strength of around 30 MPa until 40 wt % addition of G@MgO), in contrast to the noteworthy decline of tensile strength for MgO-filled composites with over 20 wt.% fillers.

Improving Catalyst Activity in Hydrocarbon Functionalization by Remote Pyrene-Graphene Stacking.

A copper complex bearing an N-heterocyclic carbene ligand with a pyrene "tail" attached to the backbone has been prepared and supported on reduced graphene oxide (rGO). The free and supported copper materials have been employed as homogeneous and heterogeneous catalysts in the functionalization of hydrocarbons such as n-hexane, cyclohexane, and benzene through incorporation of the CHCO2 Et unit from ethyl diazoacetate. The graphene-anchored complex displays higher reaction rates and induces higher yields than its soluble counterpart, features that can be rationalized in terms of a decrease in electron density at the metal center due to a remote net electronic flux from the supported copper complex to the graphene surface.

Controlled Island Formation of Large-Area Graphene Sheets by Atmospheric Chemical Vapor Deposition: Role of Natural Camphor.

Camphor-based mono-/bilayer graphene (MLG) sheets have been synthesized by very facile atmospheric chemical vapor deposition processes on Si/SiO2, soda lime glass, and flexible polyethylene terephthalate films. The effect of camphor concentration with respect to distance between camphor and the Cu foil (D) has been varied to investigate the controlled formation of a homogeneous graphene sheet over a large area on Cu foil. Raman studies show a remarkable effect of camphor at a typical distance (D) to form a monolayer to multilayer graphene (MULG) sheet. The signature of MLG to MULG sheets appears due to increase in the number of nucleation sites, even over the subsequent domains that contribute stacks of graphene over each other as observed by high-resolution transmission electron microscopy images. Moreover, the increase in camphor concentration at a particular distance generates more defect states in graphene as denoted by D band at 1360 cm–1. Uniform distribution of large-area MLG demonstrates an intense 2D/G ratio of ∼2.3. Electrical and optical measurements show a sheet resistance of ∼1 kΩ/sq with a maximum transmittance of ∼88% at 550 nm for low camphor concentration. An improvement in the rectification and photodiode behavior is observed from the diodes fabricated on n-Si/MULG as compared to n-Si/MLG in dark and light conditions.

Direct Ink Writing of Adjustable Electrochemical Energy Storage Device with High Gravimetric Energy Densities

Abstract3D printing graphene aerogel with periodic microlattices has great prospects for various practical applications due to their low density, large surface area, high porosity, excellent electrical conductivity, good elasticity, and designed lattice structures. However, the low specific capacitance limits their development in energy storage fields due to the stacking of graphene. Therefore, constructing a graphene‐based 2D materials hybridization aerogel that consists of the pseduocapacitive substance and graphene material is necessary for enhancing electrochemical performance. Herein, 3D printing periodic graphene‐based composite hybrid aerogel microlattices (HAMs) are reported via 3D printing direct ink writing technology. The rich porous structure, high electrical conductivity, and highly interconnected networks of the HAMs aid electron and ion transport, further enabling excellent capacitive performance for supercapacitors. An asymmetric supercapacitor device is assembled by two different 4‐mm‐thick electrodes, which can yield high gravimetric specific capacitance (Cg) of 149.71 F g−1 at a current density of 0.5 A g−1 and gravimetric energy density (Eg) of 52.64 Wh kg−1, and retains a capacitance retention of 95.5% after 10 000 cycles. This work provides a general strategy for designing the graphene‐based mixed‐dimensional hybrid architectures, which can be utilized in energy storage fields.

Investigation on the Tensile Behavior of Graphene-Aluminum Nano-Laminated Composites by Molecular Dynamics Simulation

Graphene-aluminum (Gr/Al) composite laminated by aluminum (Al) and graphene sheets alternately has excellent mechanical properties thanks to the high strength, high Young’s modulus and the two-dimensional atomic structure of graphene. In this study, the uniaxial tensile properties of Gr/Al nano-laminated composite are studied by molecular dynamics (MD) method. It is found that the thickness of Al layer has a significant effect on the tensile strength and Yang’s modulus of the Gr/Al composite. Composite with a smaller thickness of Al layer shows better properties. Graphene not only block propagation of dislocations, but bear most of the loads, resulting in higher Young's modulus, tensile strength and failure strain of the composites than those of pure Al. The simulation of temperature-effect shows that the Gr/Al composite is difficult to arise plastic deformation at low temperature, which lead to a higher strength and modulus of the composite. In addition, the effect of graphene stacking on the properties of composites is investigated. Through tensile tests at the vertical and parallel interfaces, it is found that graphene stacking may lead to a reduced performance of the composite.

Recent Mechanistic Understanding of Oxygen Reduction Reaction over Pt-Supported 3D Carbon Nanofiber Catalysts

For both proton exchange membrane and direct methanol fuel cells, oxygen reduction reaction (ORR) is a performance-determining step. While Pt has been established as a standard bearer in ORR catalyst development, practical long-term applications require continuing effort to pursue active, stable, as well as affordable materials as alternatives to precious metals. In this talk, carbon-based vertically aligned carbon nanofibers (VACNFs), essentially a stack of conical graphitic structures, will be discussed as highly promising ORR catalysts. In an alkaline medium, at -0.4 V applied potential, the current density measured on VACNF cathode is twice more than that measured with commercial Pt catalyst (Pt/C). Molecular insights have been gained through the use of Density functional theory (DFT) calculations to: (1) reveal interactions of ORR intermediate species at the catalytically active sites; and (2) elucidate the origin of catalytic activities of VACNF under reaction conditions. Specifically, semi-periodic fishbone-like stacked graphene sheets, bare or terminated with H and OH, have been employed to understand the impact on ORR mechanism and corresponding reactivities. Bindings of O2, O, and OH at various configurations obtained from DFT are then used as descriptors to assess catalyst performance against simple Pt (111) and Pt (211) surfaces. In addition, Pt nanocatalysts supported on VACNF (Pt/VACNF), which can push the ORR current density even higher, will be discussed as well. Again, with DFT, a model with Pt anchored at the VACNF edges was proposed to investigate the functionalities of Pt/VACNF for alkaline ORR reactions. In this talk, both associative and dissociative ORR pathways will be analyzed based on the established models. In particular, the overall computed ORR thermodynamics are shown to be favored toward Pt/VACNF than Pt (111), consistent with experimental results. Nevertheless, the unique interactions of ORR intermediates such as O*, OOH*, and OH* with catalytic active VACNF edge sites, revealed by DFT calculations, suggest intriguing but also complex electrochemistries.

Opto-electronic properties of twisted bilayer graphene quantum dots

The electronic and interband optical properties of vertically coupled stacked graphene quantum dots are investigated using the tight-binding method. Both zigzag and armchair edge configurations are taken into account. In particular, the effect of the geometrical shape (triangular or circle-like) and, most prominently, of the angle of twisting between layers is mainly addressed. The optical response is analyzed from the calculated imaginary part of the dielectric function. It is found that the interband absorption threshold is highly dependent on the dot size and geometry: For armchair triangular bilayer graphene dots the optical gap exhibits a moderate increase for smaller angles of twisting, and the structure behaves as an intermediate to a wide gap semiconductor; whereas zigzag triangular bilayer graphene dots are small gap systems in which the twisting causes the appearance of zero-gap states associated with the variation of HOMO and LUMO states resulting from the breaking of zero-energy degeneracy. In the latter case, it is shown that the low-energy transitions between those states are responsible for the main optical response of the structures which indicates possible applications in the THz optoelectronics. Circular dots are chosen in commensurable configurations and also show stronger low-energy absorption thresholds. A particular feature appearing in this case is the presence of Bravais-Moiré patterns in the two-dimensional probability density distributions for large enough dot radii.

Enhancing the electrochemical performance of lithium ion battery anodes by poly(acrylonitrile–butyl acrylate)/graphene nanoplatelet composite binder

Graphene nanoplatelet (GnP), which consists of small stacks of graphene, is used as a reinforcement to enhance the performance of the poly(acrylonitrile-butyl acrylate) (PANBA) binder in a lithium ion battery (LIB). To the best of our knowledge, this is the first time that a conductive nanofiller such as GnP has been used in a conventional water-dispersed polymer and applied as a binder for LIB. Our so-called PANBA/GnP nanocomposites are made with either 0.5 wt%, 1 wt%, or 2 wt% of GnP. The nanocomposites are synthesized via an in situ emulsion polymerization technique and are very well-dispersed, homogeneous, and stable for at least 6 months. The elongation and electrical conductivity of the PANBA/GnP nanocomposites exceed those of the PANBA non-filled polymer, and the PANBA/GnP nanocomposite binder ultimately enhances the electrochemical performance of the high-capacity silicon/graphite mixture anode.

Potassium-doped n-type stacked graphene layers

Potassium (K)-doped n-type stacked graphene layers were fabricated by repeating wet-transfer process of thermal chemical vapor deposited (CVD) single layer graphene and by dipping the samples in potassium hydroxide (KOH). Peaks due to potassium were confirmed by x-ray photoelectron spectroscopy. It was speculated, from the results of Raman spectroscopy, that stacked two layers were formed. Negative shift of Dirac point was obtained by the KOH treatments, which indicated that the obtained K-doped stacked graphene layers showed n-type conduction. Carrier mobilities were increased by the KOH treatments.

Heating induced nanostructure and superlubricity evolution of fullerene-like hydrogenated carbon films

Fullerene-like hydrogenated carbon (FL-C:H) films hold superlubricity properties at room condition, which important for saving energy, for engine use, however, high temperature serving (below 500 °C) are needed considering. In this paper, FL-C:H films were annealed with protecting of nitrogen. The tribological test show that all films have superlubricity properties, of which friction coefficient are 0.008 (200 °C), 0.005 (250 °C), 0.004 (300 °C), 0.005 (400 °C), 0.004 (500 °C), respectively. In addition, the hardness is incremental when the annealed temperature increased from 200 to 300 °C, and decremental from 300 °C to 500 °C. Interestingly, the changes of hydrogen content can be neglect in present work. Combined HRTEM, Raman spectra and XPS results, one can speculate that the degree of order for FL-C:H films increase along with the argument of annealed temperature, but competition of growth and ordering of short-chain hydrocarbon and graphene stacks that determine the hardness and H3/E2 ratio, which further influences the wear volumes. However, the friction coefficient only depends on curved grahene which can formation scroll graphene between contact surface to low friction force.

Asymmetry-enriched electronic and optical properties of bilayer graphene

The electronic and optical response of Bernal stacked bilayer graphene with geometry modulation and gate voltage are studied. The broken symmetry in sublattices, one dimensional periodicity perpendicular to the domain wall and out-of-plane axis introduces substantial changes of wavefunctions, such as gapless topological protected states, standing waves with bonding and anti-bonding characteristics, rich structures in density of states and optical spectra. The wavefunctions present well-behaved standing waves in pure system and complicated node structures in geometry-modulated system. The optical absorption spectra show forbidden optical excitation channels, prominent asymmetric absorption peaks, and dramatic variations in absorption structures. These results provide that the geometry-modulated structure with tunable gate voltage could be used for electronic and optical manipulation in future graphene-based devices.

Theory of optically induced Förster coupling in van der Waals coupled heterostructures

We investigate the impact of optically induced F\"orster coupling in van der Waals heterostructures consisting of graphene and a monolayer transition metal dichalcogenide (TMD). In particular, we predict the corresponding dephasing rates and a fast energy transfer between the TMD layer and graphene being in the picosecond range. Exemplary we find a transition rate of thermalized excitons of about 4 ps$^{-1}$ in a MoSe$_2$-graphene stack at room temperature. This timescale is in good agreement with the recently measured exciton lifetime in this heterostructure.

Tailoring Lithium Deposition via an SEI‐Functionalized Membrane Derived from LiF Decorated Layered Carbon Structure

AbstractLithium (Li) metal is a key anode material for constructing next generation high energy density batteries. However, dendritic Li deposition and unstable solid electrolyte interphase (SEI) layers still prevent practical application of Li metal anodes. In this work, it is demonstrated that an uniform Li coating can be achieved in a lithium fluoride (LiF) decorated layered structure of stacked graphene (SG), leading to the formation of an SEI‐functionalized membrane that retards electron transfer by three orders of magnitude to avoid undesirable Li deposition on the top surface, and ameliorates Li+ ion migration to enable uniform and dendrite‐free Li deposition beneath such an interlayer. Surface chemistry analysis and density functional theory calculations demonstrate that these beneficial features arise from the formation of C–Fx surface components on the SG sheets during the Li coating process. Based on such an SEI‐functionalized membrane, stable cycling at high current densities up to 3 mA cm−2 and Li plating capacities up to 4 mAh cm−2 can be realized in LiPF6/carbonate electrolytes. This work elucidates the promising strategy of modifying Li plating behavior through the SEI‐functionalized carbon structure, with significantly improved cycling stability of rechargeable Li metal anodes.

Structure and mechanical properties of GR/UHMWPE nanocomposite ropes

Ultra-high molecular weight polyethylene (UHMWPE) and graphene (GR) was melt compounded by reactive extrusion. Nanocomposite monofilaments were prepared by melt spinning through a co-rotating screw extruder and drawing at hot water. GR/UHMWPE nanocomposite ropes were twisted using nanocomposite monofilaments. A structure and mechanical properties of the GR/UHMWPE nanocomposite monofilaments and its ropes had been characterized by scanning electron microscopy (SEM), and mechanical test. Results showed that the monofilaments surface of monofilaments became rougher with introducing of GR nanosheets, which could be related to stacking of GR. The breaking load of GR/UHMWPE nanocomposite ropes was remarkably improved upon nanofiller addition, with the decrease of the elongation at break.

Finite element analysis of the effect of interlayer on interfacial stress transfer in layered graphene nanocomposites

Understanding the roles of interlayers in reinforcement efficiencies by layered graphene is very important in order to produce strong and light graphene based nanocomposites. The present paper uses the finite element method to evaluate the interfacial strain transfers and reinforcement efficiencies in layered graphene-polymer composites. Results indicate that the presence of compliant interlayers in layered graphene plays significant roles in the transfers of strain/stress from matrix to graphene and subsequently the reinforcement effectiveness of layered graphene. In general, the magnitude of shear strain transferred onto the rigid graphene decreases as the thickness of the interlayer increases. This trend becomes insignificant as the graphene becomes sufficiently large (s>25,000). The shear strain at the interface of graphene-matrix is also greatly influenced by the interlayer modulus. A stiffer interlayer would result in a higher shear strain transferred on the graphene. The performance of the interlayers is further affected by the property of the composite and the architecture of the layered graphene stack. If a composite contains more graphene phase, the efficiency of reinforcement by a layered graphene becomes improved. If a graphene stack contains more interlayers, the effectiveness of reinforcement at the edges of the graphene becomes negatively affected.

Fabrication of Stacked Graphene Oxide Nanosheet Membranes Using Triethanolamine as a Crosslinker and Mild Reducing Agent for Water Treatment.

Two-dimensional (2D) nanosheets show promise for the development of water treatment membranes with extraordinary separation properties and the advantages of atomic thickness with micrometer-sized lateral dimensions. Stacked graphene oxide (GO)-based membranes can demonstrate unique molecular sieving properties with fast water permeation. However, improvements to the structural stability of the membranes in water to avoid problems such as swelling, disruption of the ordered GO layer and decreased rejection are crucial issues. This study reports the fabrication of stacked GO nanosheet membranes by simple vacuum filtration using triethanolamine (TEOA) as a crosslinker and mild reducing agent for improved structural stability and membrane performance. Results show that GO membranes modified with TEOA (GO-TEOA membranes) have a higher structural stability in water than unmodified GO membranes, resulting in improved salt rejection performance. Furthermore, GO-TEOA membranes show stable water permeance at applied pressures up to 9 bar with Na2SO4 rejection of 85%, suggesting the potential benefits for water treatment applications.