Understanding an Exceptionally Fast and Stable Li-Ion Charging of Highly Fluorinated Graphene with Fine-Controlled C-F Configuration.

Fluorine (F) atoms with the highest electronegativity and low polarizability can easily modify the surface and composition of carbon-based electrode materials. However, this is accompanied by complete irreversibility and uncontrolled reactivity, thus hindering their use in rechargeable electronic devices. Therefore, understanding the electrochemical effects of the C-F configuration might lead to achieving superior electrochemical properties. Here, we demonstrate that the fluorinated and simultaneously reduced graphene oxide (FrGO) was easily synthesized through direct gas fluorination. The as-prepared 11%-FrGO electrode exhibited a high capacity (1365 mAh g-1 at 0.1 A g-1), remarkable rate capability, and good stability (64% retention after 1000 cycles at 5 A g-1). Furthermore, the annealed FrGO (11%-FrGO(A)) electrode in which the C-F bond configurations were controlled by facile thermal treatment shows long-term stability (80% retention after 1000 cycles at 5 A g-1). Above a certain content, F atoms enhance Li-ion adsorption and electron transfer, accelerate Li-ion diffusion, and facilitate the formation of a solid electrolyte interphase layer. In particular, the C-F configuration plays a significant role in retaining the capacity under harsh recharging conditions. The results in this study could provide valuable insights into the field of rechargeable devices.

Unusual Thermal Conductivity of Carbon Nanosheets with Self-Emerged Graphitic Carbon Dots.

The thermal conductivity (κ) of two-dimensional conducting and transparent carbon nanosheets (CNSs) prepared by a catalyst- and transfer-free process is calculated for the first time by the optothermal Raman technique. A systematic structural analysis of CNSs reveals that the thickness of polymer films affects the interaction between molecules and a Si wafer significantly, thus helping to determine the ratio of sp2 and sp3 bonding configurations of carbon (C) atoms in the CNS. Notably, the holding time of carbonization can realize a hierarchical structure with graphitic carbon dots emerging from the CNS through the rearrangement of carbon atoms, leading to the excellent κ value of 540 W/(m·K) at 310 K. It is demonstrated that an appropriate increase in carbonization time can be an effective approach for improving the ratio of sp2- to sp3-bonded C atoms in the CNS. The thermal conductivity of the CNS with the highest ratio of sp2- to sp3-bonded C atoms exhibits superior behavior and is comparable to that of reduced graphene oxide and supported graphene, respectively. Finally, when the CNS with the highest κ value of 540 W/(m·K) was applied to a heater as the heat-dissipating material, the heater showed the temperature decrease by 14 °C compared to the case without the CNS. The catalyst- and transfer-free approach for the synthesis of CNSs is highly desirable for use as heat sink materials or substrates with heat dissipation functions for extensively integrated electronic devices.

In Situ Self-Formed Nanosheet MoS3/Reduced Graphene Oxide Material Showing Superior Performance as a Lithium-Ion Battery Cathode.

Although lithium-sulfur (Li-S) batteries have 5-10 times higher theoretical capacity (1675 mAh g-1) than present commercial lithium-ion batteries, Li-S batteries show a rapid and continuous capacity fading due to the polysulfide dissolution in common electrolytes. Here, we propose the use of a sulfur-based cathode material, amorphous MoS3 and reduced graphene oxide (r-GO) composite, which can be substituted for the pure sulfur-based cathodes. In order to enhance kinetics and stability of the electrodes, we intentionally pulverize the microsized MoS3 sheet into nanosheets and form an ultrathin nano-SEI on the surface using in situ electrochemical methods. Then, the pulverized nanosheets are securely anchored by the oxygen functional group of r-GO. As a result, the electrochemically treated MoS3/r-GO electrode shows superior performance that surpasses pure sulfur-based electrodes; it exhibits a capacity of about 900 mAh g-1 at a rate of 5C for 2500 cycles without capacity fading. Moreover, a full-cell battery employing the MoS3/r-GO cathode with a silicon-carbon composite anode displays a 3-5 times higher energy density (1725 Wh kg-1/7100 Wh L-1) than present LIBs.

Observation of negative differential resistance in mesoscopic graphene oxide devices.

The fractions of various functional groups in graphene oxide (GO) are directly related to its electrical and chemical properties and can be controlled by various reduction methods like thermal, chemical and optical. However, a method with sufficient controllability to regulate the reduction process has been missing. In this work, a hybrid method of thermal and joule heating processes is demonstrated where a progressive control of the ratio of various functional groups can be achieved in a localized area. With this precise control of carbon-oxygen ratio, negative differential resistance (NDR) is observed in the current-voltage characteristics of a two-terminal device in the ambient environment due to charge-activated electrochemical reactions at the GO surface. This experimental observation correlates with the optical and chemical characterizations. This NDR behavior offers new opportunities for the fabrication and application of such novel electronic devices in a wide range of devices applications including switches and oscillators.

Reinforced PEI/PVdF Multicore-Shell Structure Composite Membranes by Phase Prediction on a Ternary Solution.

To construct a polyetherimide (PEI)-reinforced polyvinylidene fluoride (PVdF) composite membrane with multicore-shell structure, a ternary solution was prepared and electrospun by single-nozzle electrospinning. A theoretical prediction was made for the feasibility of complete distinction of two phases. The diameters of the membrane fibers and the PEI multi-core fibrils varied with the PEI ratio and the spinning time, respectively. The tensile strength and modulus were improved to 48 MPa and 1.5 GPa, respectively. The shrinkage of the membrane was only 6.6% at 180 °C, at which temperature the commercial PE separator melted down. The reinforcement in mechanical and thermal properties is associated with multiple PEI nanofibrils oriented along the fiber axis. Indeed, the unique morphology of self-assembled multicore-shell fibers plays an important role in their properties. All in all, PEI/PVdF membranes are appropriate for a lithium-ion battery application due to their high mechanical strength, excellent thermal stability, and controllable textural properties.

Glucose oxidase and polyacrylic acid based water swellable enzyme-polymer conjugates for promoting glucose detection.

Glucose oxidase (GOx) and polyacrylic acid (PAA) based water swellable non-toxic enzyme-polymer conjugate (PAA-GOx) was immobilized on a substrate consisting of graphene oxide (GO) and polyethyleneimine (PEI) (GO-PEI) and the electrochemical performances of the new catalyst were investigated. According to the measurements, although the amount of GOx immobilized on PAA-GOx was lower than that on glutaraldehyde (GA)-GOx, which is a conventionally used conjugate, its catalytic activity was 9.6 times higher than that of GA-GOx. The superior catalytic activity (102.0 µA cm-2, 20 mM of glucose) and glucose sensitivity (6.9 µA cm-2 mM-1) were due to its high swellability in water. Due to this, the PAA-GOx absorbs a large amount of aqueous glucose molecules and rapidly transfers them to the active site of GOx. Desirable hydrogen peroxide and glucose oxidation reactions are accordingly promoted. In addition, since PAA has abundant free carboxylic acid groups, the PAA-GOx forms covalent bonds with the GO-PEI to curtail the leaching-out of GOx molecules.

Synergetic effects of solution-processable fluorinated graphene and PEDOT as a hole-transporting layer for highly efficient and stable normal-structure perovskite solar cells.

We demonstrate that a bi-interlayer consisting of water-free poly(3,4-ethylenedioxythiophene) (PEDOT) and fluorinated reduced graphene oxide (FrGO) noticeably enhances the efficiency and the stability of the normal-structure perovskite solar cells (PeSCs). With simple and low temperature solution-processing, the PeSC employing the PEDOT + FrGO interlayer exhibits a significantly improved power conversion efficiency (PCE) of 14.9%. Comprehensive investigations indicate that the enhanced PCE is mostly attributed to the retarded recombination in the devices. The minimized recombination phenomena are related to the interfacial dipoles at the PEDOT/FrGO interface, which facilitates the electron-blocking and the higher built-in potential in the devices. Furthermore, the PEDOT + FrGO device shows a better stability by maintaining 70% of the initial PCE over the 30 days exposure to ambient conditions. This is because the more hydrophobic graphitic sheets of the FrGO on the PEDOT further protect the perovskite films from oxygen/water penetration. Consequently, the introduction of composite interfacial layers including graphene derivatives can be an effective and versatile strategy for high-performing, stable, and cost-effective PeSCs.

One-Step Printable Perovskite Films Fabricated under Ambient Conditions for Efficient and Reproducible Solar Cells.

Despite the potential of roll-to-roll processing for the fabrication of perovskite films, the realization of highly efficient and reproducible perovskite solar cells (PeSCs) through continuous coating techniques and low-temperature processing is still challenging. Here, we demonstrate that efficient and reliable CH3NH3PbI3 (MAPbI3) films fabricated by a printing process can be achieved through synergetic effects of binary processing additives, N-cyclohexyl-2-pyrrolidone (CHP) and dimethyl sulfoxide (DMSO). Notably, these perovskite films are deposited from premixed perovskite solutions for facile one-step processing under a room-temperature and ambient atmosphere. The CHP molecules result in the uniform and homogeneous perovskite films even in the one-step slot-die system, which originate from the high boiling point and low vapor pressure of CHP. Meanwhile, the DMSO molecules facilitate the growth of perovskite grains by forming intermediate states with the perovskite precursor molecules. Consequently, fully printed PeSC based on the binary additive system exhibits a high PCE of 12.56% with a high reproducibility.

Molybdenum disulfide nanoparticles decorated reduced graphene oxide: highly sensitive and selective hydrogen sensor.

In this work, we report on the hydrogen (H2) sensing behavior of reduced graphene oxide (RGO)/molybdenum disulfide (MoS2) nano particles (NPs) based composite film. The RGO/MoS2 composite exhibited a highly enhanced H2 response (∼15.6%) for 200 ppm at an operating temperature of 60 °C. Furthermore, the RGO/MoS2 composite showed excellent selectivity to H2 with respect to ammonia (NH3) and nitric oxide (NO) which are highly reactive gas species. The composite's response to H2 is 2.9 times higher than that of NH3 whereas for NO it is 3.5. This highly improved H2 sensing response and selectivity of RGO/MoS2 at low operating temperatures were attributed to the structural integration of MoS2 nanoparticles in the nanochannels and pores in the RGO layer.

Bi-axial grown amorphous MoSx bridged with oxygen on r-GO as a superior stable and efficient nonprecious catalyst for hydrogen evolution.

Amorphous molybdenum sulfide (MoSx) is covalently anchored to reduced graphene oxide (r-GO) via a simple one-pot reaction, thereby inducing the reduction of GO and simultaneous doping of heteroatoms on the GO. The oxygen atoms form a bridged between MoSx and GO and play a crucial role in the fine dispersion of the MoSx particles, control of planar MoSx growth, and increase of exposed active sulfur sites. This bridging leads to highly efficient (-157 mV overpotential and 41 mV/decade Tafel slope) and stable (95% versus initial activity after 1000 cycles) electrocatalyst for hydrogen evolution.

Multicore-shell nanofiber architecture of polyimide/polyvinylidene fluoride blend for thermal and long-term stability of lithium ion battery separator.

Li-ion battery, separator, multicoreshell structure, thermal stability, long-term stability. A nanofibrous membrane with multiple cores of polyimide (PI) in the shell of polyvinylidene fluoride (PVdF) was prepared using a facile one-pot electrospinning technique with a single nozzle. Unique multicore-shell (MCS) structure of the electrospun composite fibers was obtained, which resulted from electrospinning a phase-separated polymer composite solution. Multiple PI core fibrils with high molecular orientation were well-embedded across the cross-section and contributed remarkable thermal stabilities to the MCS membrane. Thus, no outbreaks were found in its dimension and ionic resistance up to 200 and 250 °C, respectively. Moreover, the MCS membrane (at ~200 °C), as a lithium ion battery (LIB) separator, showed superior thermal and electrochemical stabilities compared with a widely used commercial separator (~120 °C). The average capacity decay rate of LIB for 500 cycles was calculated to be approximately 0.030 mAh/g/cycle. This value demonstrated exceptional long-term stability compared with commercial LIBs and with two other types (single core-shell and co-electrospun separators incorporating with functionalized TiO2) of PI/PVdF composite separators. The proper architecture and synergy effects of multiple PI nanofibrils as a thermally stable polymer in the PVdF shell as electrolyte compatible polymers are responsible for the superior thermal performance and long-term stability of the LIB.

Comprehensive stabilization mechanism of electron-beam irradiated polyacrylonitrile fibers to shorten the conventional thermal treatment.

An electron beam was irradiated on polyacrylonitrile (PAN) fibers prior to thermal stabilization. The electron-beam irradiation effectively shortened the thermal stabilization process by one fourth compared with the conventional thermal stabilization process. A comprehensive mechanistic study was conducted regarding this shortening of the thermal stabilization by electron-beam irradiation. Various species of chain radicals were produced in PAN fibers by electron-beam irradiation and existed for a relatively long duration, as observed by electron spin resonance spectroscopy. Subsequently, these radicals were gradually oxidized to peroxy radicals in the presence of oxygen under storage or heating. We found that these peroxy radicals (CO) enabled such an effective shortcut of thermal stabilization by acting as intermolecular cross-linking and partial aromatization points in the low temperature range (100-130 °C) and as earlier initiation seeds of successive cyclization reactions in the next temperature range (>130-140 °C) of thermal stabilization. Finally, even at a low irradiation dose (200 kGy), followed by a short heat treatment (230 °C for 30 min), the PAN fibers were sufficiently stabilized to produce carbon fibers with tensile strength and modulus of 2.3 and 216 GPa, respectively, after carbonization.

Strengthened PAN-based carbon fibers obtained by slow heating rate carbonization.

Large efforts have been made over the last 40 years to increase the mechanical strength of polyacrylonitrile (PAN)-based carbon fibers (CFs) using a variety of chemical or physical protocols. In this paper, we report a new method to increase CFs mechanical strength using a slow heating rate during the carbonization process. This new approach increases both the carbon sp(3) bonding and the number of nitrogen atoms with quaternary bonding in the hexagonal carbon network. Theoretical calculations support a crosslinking model promoted by the interstitial carbon atoms located in the graphitic interlayer spaces. The improvement in mechanical performance by a controlled crosslinking between the carbon hexagonal layers of the PAN based CFs is a new concept that can contribute further in the tailoring of CFs performance based on the understanding of their microstructure down to the atomic scale.

Alternating Current Dielectrophoresis Optimization of Pt-Decorated Graphene Oxide Nanostructures for Proficient Hydrogen Gas Sensor.

Alternating current dielectrophoresis (DEP) is an excellent technique to assemble nanoscale materials. For efficient DEP, the optimization of the key parameters like peak-to-peak voltage, applied frequency, and processing time is required for good device. In this work, we have assembled graphene oxide (GO) nanostructures mixed with platinum (Pt) nanoparticles between the micro gap electrodes for a proficient hydrogen gas sensors. The Pt-decorated GO nanostructures were well located between a pair of prepatterned Ti/Au electrodes by controlling the DEP technique with the optimized parameters and subsequently thermally reduced before sensing. The device fabricated using the DEP technique with the optimized parameters showed relatively high sensitivity (∼10%) to 200 ppm hydrogen gas at room temperature. The results indicates that the device could be used in several industry applications, such as gas storage and leak detection.

Ultra-high dispersion of graphene in polymer composite via solvent free fabrication and functionalization.

The drying process of graphene-polymer composites fabricated by solution-processing for excellent dispersion is time consuming and suffers from a restacking problem. Here, we have developed an innovative method to fabricate polymer composites with well dispersed graphene particles in the matrix resin by using solvent free powder mixing and in-situ polymerization of a low viscosity oligomer resin. We also prepared composites filled with up to 20 wt% of graphene particles by the solvent free process while maintaining a high degree of dispersion. The electrical conductivity of the composite, one of the most significant properties affected by the dispersion, was consistent with the theoretically obtained effective electrical conductivity based on the mean field micromechanical analysis with the Mori-Tanaka model assuming ideal dispersion. It can be confirmed by looking at the statistical results of the filler-to-filler distance obtained from the digital processing of the fracture surface images that the various oxygenated functional groups of graphene oxide can help improve the dispersion of the filler and that the introduction of large phenyl groups to the graphene basal plane has a positive effect on the dispersion.

Oxygen adsorption-induced surface segregation of titanium oxide by activation in carbon nanofibers for maximizing photocatalytic performance.

This research demonstrates a simple method for synthesizing titanium dioxide nanoparticle-decorated carbon nanofibers. These nanofibers showed highly efficient degradation of methylene blue under UV light because of the synergistic effects of the large surface-active sites of titanium dioxide nanoparticles and the carbon nanofibers on the photocatalytic properties.

FTO-free counter electrodes for dye-sensitized solar cells using carbon nanosheets synthesised from a polymeric carbon source.

Highly conductive carbon nanosheets (CNSs) are fabricated using a polymeric carbon source and subsequently applied as the counter electrodes (CNS-CEs) for dye-sensitized solar cells (DSSCs). The CNSs have a similar structure to multilayered graphene, and their high electrical conductivity and electrocatalytic activity enable them to have a dual-function as both CEs and charge supporting electrodes. CNSs form a unique CE material that functions successfully while being metal- and fluorine doped tin oxide (FTO)-free and allowing DSSCs to achieve ∼5% power conversion efficiency. The chemical structure, electrical properties, electrocatalytic activity, and work function of the CNS-CEs prepared under various conditions of carbonization are investigated, and their effects on the performance of the corresponding DSSCs are discussed. Carbonization temperature is shown to have influenced the size of graphitic domains and the presence of heteroatoms and functional groups in CNS-CEs. The change in the graphitic domain size has a marginal influence on the work function of the CNS-CEs and the overpotential for the reduction of the redox couples (I(-)/I3(-)). However, the electrical conductivity of CNS-CEs and the charge transfer resistance at CE/electrolyte interfaces in the DSSCs are considerably influenced by the carbonization condition. Our study shows that CNSs serve as efficient, FTO-free CE materials for DSSCs, and they are appropriate materials with which the effects of the chemical/physical properties of graphene-based materials on the electrode performance of various electrochemical devices may be studied.

Fluorine-functionalized and simultaneously reduced graphene oxide as a novel hole transporting layer for highly efficient and stable organic photovoltaic cells.

A one-step reduction and functionalization of graphene oxide (FrGO) was easily achieved using a novel phenylhydrazine-based reductant containing fluorine atoms, which can induce p-type doping due to its high electronegativity. The FrGO-based OPV exhibited a high power conversion efficiency of ∼6.71% and a superior OPV-stability to commercial PEDOT:PSS.

Network formation in graphene oxide composites with surface grafted PNIPAM chains in aqueous solution characterized by rheological experiments.

Poly N-isopropyl acrylamide (PNI) radically polymerized in aqueous solution in the presence of graphene oxide (GO) can significantly change the properties of the resulting solution from a regular polymer solution to a soft solid with a GO content of only 0.176 wt% (3 wt% with respect to PNI). However, these properties require the presence of both grafting and supramolecular interactions between polymer chains and hydrophilic groups on GO (-OH, -COOH), proven by Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), X-ray diffraction and spectroscopy (XRD) and Raman spectra. While very low GO-contents (below 0.05 wt%) only lead to a labile structure, which can be disassembled by shear, higher contents yield composites with solid-like characteristics. This is clearly evident from the rheological behaviour, which changes significantly at a GO content around 0.15 wt%. Intensive shearing destroys the weak network, which cannot reform quickly at lower GO-concentrations, while at intermediate concentrations, restructuring is fast. GO-contents of 0.176 wt% lead to a material behaviour, which almost perfectly recovers from small deformations (creep and creep recovery compliance almost match) but larger deformations lead to permanent damage to the sample.