The rapid and enhanced reduction of graphene oxide by microwave assisted acid catalyzed reaction.

We report a novel synthetic route to fabricate reduced graphene oxide (rGO) from graphene oxide (GO) using a microwave assisted acid catalyzed reaction in organic solvent. The obtained rGO in this study exhibited 4 times higher electrical conductivity, less oxygen content and better ordered structure than that of conventional solvothermally fabricated ones. By using microwave irradiation, high quality rGO can be obtained in several minutes.

In situ synthesis and cell performance of a Si/C core-shell/ball-milled graphite composite for lithium ion batteries.

A high-capacity silicon-carbon core-shell (Si/C) supported by ball-milled graphite (BMG) was synthesized in situ using a hydrosilylation reaction and tested as an anode material for lithium ion batteries (LIBs) in the investigation of the effects of dual buffer layers of carbon shell and BMG. The Si/C/BMG sample effectively absorbed high volumetric expansion/contraction generated during charge/discharge process due to the assistance of dual elastic buffers of carbon shell and BMG. As a result, after 50 charge/discharge cycles, the Si/C/BMG electrodes still had a very high capacity of 1615 mAh/g, whereas raw Si, Si/C, and a mechanical mixture of Si/C and BMG were less than 500 mAh/g. The results of various electrochemical characterization techniques revealed that the dual buffer layers were favorable in decreasing electron and ion transfer resistance. It was also shown from ex situ TEM results that the carbon layers behaved as anti-amorphization layers decreasing the amorphization rate of crystalline Si during the alloying/dealloying of Li with Si.

Nanostructured graphene/Fe3O4 incorporated polyaniline as a high performance shield against electromagnetic pollution.

The development of high-performance shielding materials against electromagnetic pollution requires mobile charge carriers and magnetic dipoles. Herein, we meet the challenge by building a three-dimensional (3D) nanostructure consisting of chemically modified graphene/Fe3O4(GF) incorporated polyaniline. Intercalated GF was synthesized by the in situ generation of Fe3O4 nanoparticles in a graphene oxide suspension followed by hydrazine reduction, and further in situ polymerization with aniline to form a polyaniline composite. Spectroscopic analysis demonstrates that the presence of GF hybrid structures facilitates strong polarization due to the formation of a solid-state charge-transfer complex between graphene and polyaniline. This provides proper impedance matching and higher dipole interaction, which leads to the high microwave absorption properties. The higher dielectric loss (ε'' = 30) and magnetic loss (µ'' = 0.2) contribute to the microwave absorption value of 26 dB (>99.7% attenuation), which was found to depend on the concentration of GF in the polyaniline matrix. Moreover, the interactions between Fe3O4, graphene and polyaniline are responsible for superior material characteristics, such as excellent environmental (chemical and thermal) degradation stability and good electric conductivity (as high as 260 S m(-1)).

Enhanced thermal conductivity of epoxy-graphene composites by using non-oxidized graphene flakes with non-covalent functionalization.

Homogeneous distribution of graphene flakes in a polymer matrix, still preserving intrinsic material properties, is key to successful composite applications. A novel approach is presented to disperse non-oxidized graphene flakes with non-covalent functionalization of 1-pyrenebutyric acid and to fabricate nanocomposites with outstanding thermal conductivity (∼1.53 W/mK) and mechanical properties (∼1.03 GPa).

SnO2 nanoparticles distributed on multi-walled carbon nanotubes and ball-milled graphite as anode materials of lithium ion batteries.

SnO2 nanoparticles were supported on ball-milled graphite (BMG) or carbon nanotubes (CNTs) using a chemical reduction method with ethylene glycol, and the electrochemical properties of the nanocomposites were evaluated as anode active materials of lithium-ion batteries. The BMG and CNTs contributed to an increase in both the capacity enhancement and cyclic stability compared to that of commercial graphite. In particular, the mixture electrode of SnO2/BMG:SnO2/CNT = 3:1 (in weight ratio) showed higher performance in the reversible capacity and cyclic stability than did the SnO2/BMG and SnO2/CNT electrodes. This might be resulted from the network formation for excellent electronic path by CNT distributed on SnO2/BMG composites.

Fast and simple reduction of graphene oxide in various organic solvents using microwave irradiation.

The fabrication of graphene has been widely studied and chemical reduction is considered the most suitable approach to achieve large-scale production and graphene functionalization due to its versatility of chemical routes. We report here a fast and simple reduction of graphene oxide in various organic solvents using microwave irradiation. The reduction can be completed in several minutes, and the oxygen content and conductivity (10,000 S/m) of the reduced graphene oxide were comparable to the previously reported results which reported between 1 hr and 24 hrs for the reduction. We also found that an amide group containing a solvent like NMP or DMF reduced graphene oxide (GO) more effectively than did other solvents. Further, free radicals generated from NMP significantly enhanced deoxygenation of graphene oxide. Moreover, this approach is a non-toxic and environmentally-friendly method to obtain highly conductive reduced GO for a wide range of applications including graphene-based composites, batteries, and electrodes for super-capacitors.

Preparation of nano-sized graphite-supported CuO and Cu-Sn as active materials in lithium ion batteries.

Nano-sized Cu-Sn and Cu oxide particles supported on ball-milled graphite were synthesized, and their electrochemical characteristics for use as anode active materials in lithium-ion batteries were investigated. The samples were also characterized via FE-SEM, XRD, and TGA. Most of the Cu oxides on BMG were monoclinic CuO crystals, whereas the Cu-Sn particles were composed of hexagonal Cu3Sn and tetragonal SnO2 crystals. These particles may contribute to an increase in the reversible capacity of lithium ion batteries.

Exfoliation of non-oxidized graphene flakes for scalable conductive film.

The increasing demand for graphene has required a new route for its mass production without causing extreme damages. Here we demonstrate a simple and cost-effective intercalation based exfoliation method for preparing high quality graphene flakes, which form a stable dispersion in organic solvents without any functionalization and surfactant. Successful intercalation of alkali metal between graphite interlayers through liquid-state diffusion from ternary KCl-NaCl-ZnCl(2) eutectic system is confirmed by X-ray diffraction and X-ray photoelectric spectroscopy. Chemical composition and morphology analyses prove that the graphene flakes preserve their intrinsic properties without any degradation. The graphene flakes remain dispersed in a mixture of pyridine and salts for more than 6 months. We apply these results to produce transparent conducting (∼930 Ω/□ at ∼75% transmission) graphene films using the modified Langmuir-Blodgett method. The overall results suggest that our method can be a scalable (>1 g/batch) and economical route for the synthesis of nonoxidized graphene flakes.

Superior dispersion of highly reduced graphene oxide in N,N-dimethylformamide.

Here, we report the effect of temperature on the extent of hydrazine reduction of graphene oxide in N,N-dimethylformamide (DMF)/water (80/20 v/v) and the dispersibility of the resultant graphene in DMF. The highly reduced graphene oxide (HRG) had a high C/O ratio and good dispersibility in DMF. The good dispersibility of HRGs is due to the solvation effect of DMF on graphene sheets during the hydrazine reduction, which diminishes the formation of irreversible graphene sheet aggregates. The dispersibility of the HRGs was varied from 1.66 to 0.38 mg/mL when the reduction temperature increased from 25 °C to 80 °C. The dispersibility of the HRGs was inversely proportional to the electrical conductivity of the HRGs, which varied from 17,400 to 25,500 S/m. The relationships between the C/O ratio, electrical conductivity, and dispersibility of the HRGs were determined and these properties were found to be easily controlled by manipulating the reduction temperature.

Electrospun core-shell fibers for robust silicon nanoparticle-based lithium ion battery anodes.

Because of its unprecedented theoretical capacity near 4000 mAh/g, which is approximately 10-fold larger compared to those of the current commercial graphite anodes, silicon has been the most promising anode for lithium ion batteries, particularly targeting large-scale energy storage applications including electrical vehicles and utility grids. Nevertheless, Si suffers from its short cycle life as well as the limitation for scalable electrode fabrication. Herein, we develop an electrospinning process to produce core-shell fiber electrodes using a dual nozzle in a scalable manner. In the core-shell fibers, commercially available nanoparticles in the core are wrapped by the carbon shell. The unique core-shell structure resolves various issues of Si anode operations, such as pulverization, vulnerable contacts between Si and carbon conductors, and an unstable sold-electrolyte interphase, thereby exhibiting outstanding cell performance: a gravimetric capacity as high as 1384 mAh/g, a 5 min discharging rate capability while retaining 721 mAh/g, and cycle life of 300 cycles with almost no capacity loss. The electrospun core-shell one-dimensional fibers suggest a new design principle for robust and scalable lithium battery electrodes suffering from volume expansion.

Recent advances in hybrids of carbon nanotube network films and nanomaterials for their potential applications as transparent conducting films.

The use of carbon nanotubes (CNTs) as transparent conducting films is one of the most promising aspects of CNT-based applications due to their high electrical conductivity, transparency, and flexibility. However, despite many efforts in this field, the conductivity of carbon nanotube network films at high transmittance is still not sufficient to replace the present electrodes, indium tin oxide (ITO), due to the contact resistances and semi-conducting nanotubes of the nanotube network films. Many studies have attempted to overcome such problems by the chemical doping and hybridization of conducting guest components by various methods, including acid treatment, deposition of metal nanoparticles, and the creation of a composite of conducting polymers. This review focuses on recent advances in surface-modified carbon nanotube networks for transparent conducting film applications. Fabrication methods will be described, and the stability of carbon nanotube network films prepared by various methods will be demonstrated.

Preparation of graphene relying on porphyrin exfoliation of graphite.

A new method for the preparation of graphene has been developed via porphyrin exfoliation of graphite in NMP. The exfoliation, which follows the intercalation of organic ammonium ions, is based on the pi-pi interaction between graphene and porphyrins. The graphene sheets prepared by this method show undisturbed sp(2) carbon networks.

Electrical conductivity of graphene films with a poly(allylamine hydrochloride) supporting layer.

The electrical conductivity of graphene oxide (GO) and reduced graphene oxide (RGO) films with poly(allylamine hydrochloride) (PAH) supporting layers is investigated. Graphene-PAH hybrid films were produced in a two-step procedure that consisted of vacuum filtration for GO (or RGO) dispersion to fabricate the graphene thin films on quartz substrates, followed by the deposition of PAH onto the graphene films via solution casting. Highly selective deposition of the PAH layer on the graphene sheets was confirmed through the detection of the fluorescence signals of hybridized Cy3-DNA onto the PAH-coated graphene surfaces. In this case, electrostatic interaction plays an important role in the selective deposition process. Interestingly, it was found that the electrical conductivity of RGO films was significantly enhanced by 120% after PAH treatment, whereas that of the GO films was reduced by 98% of its initial conductivity. This finding was interpreted in terms of the molecular structure and oxygen functionalities of GO and RGO films combined with the ionic conduction characteristics of hydrated PAH on the RGO film.

Tin nanoparticle thin film electrodes fabricated by the vacuum filtration method for enhanced battery performance.

A novel method for fabricating tin nanoparticle thin film electrodes that show good performance in lithium ion batteries during cycling is reported. The vacuum filtration method has the advantage of affording a high degree of dispersion of the electrode components, thereby providing good electrical contacts between the tin nanoparticles and the conductive carbon or current collector. The reversible capacity and initial Coulombic efficiency are 726 mA h g(-1) and 85.3%, respectively, with this thin film electrode. Cycle life performance tests under real battery conditions show that the battery capacity and reaction peaks remained stable for up to 50 cycles. SEM shows that the uniform morphology of the vacuum filtered film was maintained throughout the cycle life test. This novel vacuum filtration method for providing nanoparticle-based film electrodes has further potential applications for use in various devices such as high power, thin film batteries, supercapacitors and organic-inorganic hybrid photovoltaic cells.

Layer-by-layer assembly of graphene and gold nanoparticles by vacuum filtration and spontaneous reduction of gold ions.

Layer-by-layer films comprised of alternating graphene and gold nanoparticle layers are readily produced by the two-step procedure involving the use of vacuum filtration of a reduced graphene oxide solution to fabricate the graphene thin film on the quartz substrate, followed by gold nanoparticle formation by spontaneous reduction of gold ions in a gold salt solution on the graphene films.

Unusually large Franz-Keldysh oscillations at ultraviolet wavelengths in single-walled carbon nanotubes.

We report large electroabsorption susceptibilities in the ultraviolet region for single-walled carbon nanotubes (SWNT) supported on quartz that are approximately 10;{3} larger than the highest values reported to date for any system. The oscillatory behavior is described using a convolution of Airy functions in photon energy ascribing the effect to Franz-Keldysh oscillations. The metallic and semiconducting SWNT composition is varied, and it is shown that the confinement energy correlates with the average band gap for semiconducting SWNT in the film. The large susceptibilities arise from a subpercolated network of metallic SWNT that enhances the local electric field.