Preparation and electrochemical properties of polyaniline/reduced graphene oxide composites

Polyaniline (PANI)/reduced graphene oxide (rGO) composites were synthesized by in situ oxidative polymerization of aniline on reduced graphene sheets. Fourier transform infrared spectroscopy, X‐ray diffraction, thermogravimetric analysis, transmission electron microscopy, and scanning electron microscopy were used to characterize the composites. The results indicated PANI/rGO composites were produced and contained covalent bonds between the functional groups of PANI and rGO. A uniform coating of PANI on the rGO sheets had a synergistic effect on the properties of the composites. The electrochemical properties of the PANI/rGO composites produced using different feed ratios of aniline to rGO were studied. The results showed that the composites exhibited a maximum specific capacitance of 797.5 F/g at 0.5 A/g and minimum charge transfer resistance of 0.98 Ω when the feed ratio of aniline to rGO was 2:1. These values were superior to those of pure PANI and rGO. The composites also displayed excellent cycling stability, with specific capacitance retention of 92.43% after 1000 cycles. These stable structural composites show promise for the development of new supercapacitor applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46103.     

A comparison of thermoplastic polyurethane incorporated with graphene oxide and thermally reduced graphene oxide: Reduction is not always necessary

Despite wide applications of reduced graphene-oxide (GO)-reinforced polymer-based composites, the necessity of the reduction procedure toward GO is still controversial. In this article, thermoplastic polyurethane (TPU) composites incorporated with GO and thermally reduced graphene oxide (TGO) were fabricated. GO and TGO exhibited different effects on crystallization behaviors, and mechanical and thermal properties of the TPU matrix. With 2.0 wt % filler loading, TPU composite reinforced by GO (TPU-GO-2 wt %) exhibited better thermal stability than that reinforced by TGO (TPU-TGO-2 wt %). The interfacial interaction between the nanofillers and the TPU matrix as well as their influence on the mobility of TPU chains were investigated, which proved that GO is superior to TGO in improving interface adhesion and maintaining crystallization of the TPU matrix. Compared with TPU-TGO-2 wt %, improved mechanical properties of TPU-GO-2 wt % were also evidenced owing to more oxygen-containing groups. This work demonstrates that the reduction of GO is not always necessary in fabricating polymer composites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47745.     

Morphology and electrical conductivity of polyethylene/polypropylene blend filled with thermally reduced graphene oxide and surfactant exfoliated graphene

High‐density polyethylene (HDPE)/polypropylene (PP) composites with graphenes were prepared by melt‐compounding method. Graphene sheets were prepared through thermally reduced graphene oxide (TRG) and surfactant exfoliated graphene (SEG), respectively. Structural characterization showed that the TRG sheets exhibited a few‐layers composition with more defects compared to the SEG sheets. Morphological observations of the composites demonstrated that the graphene was preferentially dispersed in the HDPE phase and the addition of graphene (TRG and SEG) influenced the phase structure of the HDPE/PP composites. The distribution of the TRG sheets in the HDPE phase was better than the SEG sheets, and the obtained HDPE/PP composites exhibited a low electrical percolation threshold with the highly dispersed graphene. The TRG/HDPE/PP composite showed a low electrical percolation threshold of 3 wt% (1.25 vol%). For the SEG/HDPE/PP system, the percolation threshold was 7 wt% (2.98 vol%). Differences in the behavior of the two graphene components (TRG and SEG) in the HDPE/PP composites influenced the formation of percolation networks and electrical properties. POLYM. COMPOS., 38:2098–2105, 2017. © 2015 Society of Plastics Engineers     

Microwave absorbing properties of a thermally reduced graphene oxide/nitrile butadiene rubber composite

Reduced graphene oxide (RGO) with a layered and porous structure was synthesized by thermal exfoliation of graphite oxide. Synthesized RGO is very light weight and flaky. The formation of RGO was studied using Fourier transform infrared and Raman spectroscopies, X-ray diffraction and scanning electron microscopy. Composites were prepared by dispersing 2%, 4% and 10% by weight of the synthesized RGO into nitrile butadiene rubber (NBR) matrix. Microwave absorption properties of RGO/NBR composites were investigated by measuring their complex permittivity and permeability by using waveguide method. Simulation studies show that 10 wt.% of graphene oxide in NBR matrix exhibits high values of reflection loss (>10 dB) over a wide frequency range 7.5–12 GHz and maximum loss is 57 dB at 9.6 GHz at a thickness of 3 mm.     

Electrical conductivity of thermally reduced graphene oxide/polymer composites with a segregated structure

A simple method to prepare thermally reduced graphene oxide/polymer composites was developed to enhance the electrical conductivity of the polymer. Graphene oxide sheets were coated onto the surfaces of poly(vinylidene fluoride) powders and then hot pressed at 200 °C to form composites with a segregated structure. After hot-pressing, the thermally reduced graphene oxide sheets were located in the interstices among the polymer domains and formed a two-dimensional conductive network. The resulting composites exhibited excellent electrical conductivity and a low percolation threshold (0.105 vol.%).     

钛酸锂/石墨烯复合材料及电化学性能

通过固相法制备出钛酸锂(LTO)样品,再将LTO和氧化石墨烯通过水热法制得钛酸锂/还原石墨烯复合材料(LTO-RGO)。通过XRD、SEM、TEM对材料的结构、形貌进行表征,并进行充放电性能测试、交流阻抗测试来检测其电化学性能。结果表明,石墨烯对钛酸锂进行包覆处理不影响钛酸锂材料的晶型结构、无杂相出现。钛酸锂/石墨烯复合材料表现出了比钛酸锂材料更为优异的电化学性能,0.2C倍率下的放电比容量为208.7mA·h/g,50次循环后容量保持率为98.10%;20C倍率下的放电比容量为136.1mA·h/g。     

The synergistic mechanism of thermally reduced graphene oxide and antioxidant in improving the thermo-oxidative stability of polypropylene

The feasibility of using thermally reduced graphene oxide (TrGO) to improve the antioxidative efficiency of commercial antioxidant (3,5-di-tert-butyl-4-hydroxycinnamic acid, AO) on unstabilized polypropylene (PP) was evaluated in terms of the oxidation induction time (OIT) and the initial degradation temperature (T_i). It was found that a synergistic effect exist between AO and TrGO in retarding the degradation of PP in oxygen-containing atmosphere. Compared with that of PP/AO (100/0.5) sample, the OIT value of PP/AO/TrGO (100/0.5/1) composite was almost doubled at 180 °C and the value of T_i in air was improved by 37.2 °C. As verified by using radical scavenging assay with the 1,1-diphenyl-2-picrylhydrazyl radical, the TrGO sheets exhibited a good radical scavenging capacity. The synergistic stabilization mechanism was attributed to the enhanced dispersion of TrGO sheets in the PP matrix in the presence of 0.5 wt.% AO, which could improve the oxygen barrier effect and radical scavenging efficiency of TrGO. This synergistic effect between AO and TrGO can efficiently reduce the concentrations of oxygen and peroxy radicals in the PP matrix, leading to the significant improvement in thermo-oxidative stability of PP/AO/TrG composite.     

Improved electrochemical performances of reduced graphene oxide based supercapacitor using redox additive electrolyte

Reduced graphene oxide (rGO) is prepared by simple and eco-friendly hydrothermal reduction method. X-ray photoelectron spectroscopy and Ultraviolet–visible analysis corroborated the reduction of graphene oxide into rGO in basic medium. The flexibility of the prepared rGO is inferred from transmission electron micrographs. Further, the identification of suitable electrolyte is carried out using different anions (SO₄²⁻, Cl⁻, OH⁻) and cations (K⁺, Na⁺) for the superior performance of the rGO based supercapacitors. The electrochemical performance revealed that K⁺ and OH⁻ ions are more active species in aqueous solutions. Subsequently, an effort was taken to improve the specific capacitance in the optimized 1 M KOH electrolyte by KI as redox additive at different concentrations (0.025, 0.05, 0.075 and 0.1 M). The calculated specific capacitance and energy density of rGO electrode in the optimized 1 M KOH + 0.05 M KI electrolyte is 500 F g⁻¹ and 44 Wh kg⁻¹, respectively. On the other hand, it exhibited the specific capacitance of 298 F g⁻¹ at 0.83 A g⁻¹ in non-aqueous polymer gel (PVA + KOH + KI) electrolyte. Finally, the charged aqueous device is utilized to glow the light emitting diode.     

Multiscale patterning of graphene oxide and reduced graphene oxide for flexible supercapacitors

A simple and facile method for multiscale, in-plane patterning of graphene oxide and reduced graphene oxide (GO–rGO) was developed by region-specific reduction of graphene oxide (GO) under a mild irradiation. The UV-induced reduction of graphene oxide was monitored by various spectroscopic techniques, including optical absorption, X-ray photoelectron spectroscopy (XPS), Raman, and X-ray diffraction (XRD), while the resultant GO–rGO patterned film morphology was studied on optical microscope, scanning electron microscope (SEM), and atomic force microscope (AFM). Flexible symmetric and in-plane supercapacitors were fabricated from the GO–rGO patterned polyethylene terephthalate (PET) electrodes to show capacitances up to 141.2 F/g.     

Electronic structure of graphite oxide and thermally reduced graphite oxide

We present the electronic structure evolution from graphite oxide to thermally reduced graphite oxide. Most functional groups were removed by thermal reduction as indicated by high resolution X-ray photoelectron spectroscopy, and the electrical conductivity increased 6 orders compare with the precursor graphite oxide. X-ray absorption spectroscopy reveals that the thermally reduced graphite oxide shows several absorption peaks similar to those of pristine graphite, which were not observed in graphite oxide or chemically reduced graphite oxide. This indicates the better restoration of graphitic electronic conjugation by thermal reduction. Furthermore, the significant increased intensity of Raman 2D band of thermally reduced graphite oxide compared with graphite oxide also suggests the restoration of graphitic electronic structure (π orbital). These results provide useful information for fundamental understanding of the electronic structure of graphite oxide and thermally reduced graphite oxide.     

Study of the effect of thermally reduced graphene oxide on the physical and mechanical properties of flexible polyurethane foams

Flexible polyurethane (PU) foams were obtained from a two‐component system via the one‐step method. The foams were modified with thermally reduced graphene oxide added in the amount equal to 0.25, 0.5, and 0.75 wt%. The morphology, static and dynamic properties, and thermal stability of modified foams were determined. The application of carbon filler resulted in the visible increase in the cell size, apparent density, and rigidity of the modified systems, as confirmed by the measurements of glass transition temperature. Glass transition temperature increased with increasing content of nanofiller. In addition, thermally reduced graphene oxide had an effect on the thermal stability of the obtained foam systems. The addition of 0.5 wt% of nanofiller resulted in an increase in T₅ by 16°C compared with the reference foam. This study also demonstrated that after exceeding a specific content of thermally reduced graphene oxide, that is, 0.5%, the physicochemical properties of the obtained systems start to deteriorate. The research results showed that thermally reduced graphene oxide can be successfully used as a modifier of mechanical and thermal properties in flexible PU foams. POLYM. COMPOS., 38:2248–2253, 2017. © 2015 Society of Plastics Engineers     

Synthesis of reduced graphene oxide/tungsten trioxide nanocomposite electrode for high electrochemical performance

A facile and well-controllable reduced graphene oxide/tungsten trioxide (rGO/WO₃) nanocomposite electrode was successfully synthesized via an electrostatic assembly route at 350 rpm for 24 h. In this study, hexagonal-phase WO₃ (h-WO₃) nanofiber was well distributed on rGO sheets by applying optimal processing parameters. The as-synthesized rGO/WO₃ nanocomposite electrode was compared with pure h-WO₃ electrode. A maximum specific capacitance of 85.7 F g⁻¹ at a current density of 0.7 A g⁻¹ was obtained for the rGO/WO₃ nanocomposite electrode, which showed better electrochemical performance than the WO₃ electrode. The incorporation of WO₃ into rGO could prevent the restacking of rGO and provide favourable surface adsorption sites for intercalation/de-intercalation reactions. The impedance studies demonstrated that the rGO/WO₃ nanocomposite electrode exhibited lower resistance because of the superior conductivity of rGO that improved ion diffusion into the electrode. To evaluate the contribution of WO₃ to the rGO/WO₃ nanocomposite, the influence of mass loading of WO₃ on the capacitance was investigated.     

Facile synthesis of metal oxide/reduced graphene oxide hybrids with high lithium storage capacity and stable cyclability

We report an environment-friendly approach to synthesize transition metal oxide nanoparticles (NPs)/reduced graphene oxide (rGO) sheets hybrids by combining the reduction of graphene oxide (GO) with the growth of metal oxide NPs in one step. Either Fe2O3 or CoO NPs were grown onto rGO sheets in ethanol solution through a solvothermal process, during which GOs were reduced to rGO without the addition of any strong reducing agent, e.g. hydrazine, or requiring any post-high-temperature annealing process. The GO or rGO during the precipitation of metal oxide NPs may act as heterogeneous nucleation seeds to facilitate the formation of small crystal grains. This may allow more efficient diffusion of Li ions and lead to high specific capacities. These metal oxide NPs-rGO hybrids were used as anodes for Li-ion batteries, which showed high capacities and excellent charge-discharge cycling stability in the voltage window between 0.01 and 3.0 V. For example, Fe2O3 NPs/rGO hybrids showed specific capacity of 881 mA h g(-1) in the 90th cycle at a discharge current density of 302 mA g(-1) (0.3 C), while CoO NPs/rGO hybrids showed a lower capacity of 600 mA h g(-1) in the 90th cycle at a discharge current density of 215 mA g(-1) (0.3 C). These nanohybrids also show excellent capacities at high C rate currents, e.g. 611 mA h g(-1) for Fe2O3/rGO sample in the 300th cycle at 2014 mA g(-1) (2 C). Such synthesis technique can be a promising route to produce advanced electrode materials for Li-ion batteries.     

Preparation and properties of dopamine reduced graphene oxide and its composites of epoxy

To improve the thermal and mechanical properties and further to expand its applications of epoxy in electronic packaging, reduced graphene oxide/epoxy composites have been successfully prepared, in which dopamine (DA) was used as reducing agent and modifier for graphene oxide (GO) to avoid the environmentally harmful reducing agents and address the problem of aggregation of graphene in composites. Further studies revealed that DA could effectively eliminate the labile oxygen functionality of GO and generate polydopamine functionalized graphene oxide (PDA‐GO) because DA would be oxidated and undergo the rearrangement and intermolecular cross‐linking reaction to produce polydopamine (PDA), which would improve the interfacial adhesion between GO and epoxy, and further be beneficial for the homogenous dispersion of GO in epoxy matrix. The effect of PDA‐GO on the thermal and mechanical properties of PDA‐GO/epoxy composites was also investigated, and the incorporation of PDA‐GO could increase the thermal conductivity, storage modulus, glass transition (T_g), and dielectric constant of epoxy. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39754.     

Synthesis and electrochemical performance of reduced graphene oxide/maghemite composite anode for lithium ion batteries

Reduced graphene oxide (rGO) tethered with maghemite (γ-Fe₂O₃) was synthesized using a novel modified sol–gel process, where sodium dodecylbenzenesulfonate was introduced into the suspension to prevent the undesirable formation of an iron oxide 3D network. Thus, nearly monodispersed and homogeneously distributed γ-Fe₂O₃ magnetic nanoparticles could be obtained on surface of graphene sheets. The utilized thermal treatment process did not require a reducing agent for reduction of graphene oxide. The morphology and structure of the composites were investigated using various characterization techniques. As-prepared rGO/Fe₂O₃ composites were utilized as anodes for half lithium ion cells. The 40 wt.%-rGO/Fe₂O₃ composite exhibited high reversible capacity of 690 mA h g⁻¹ at current density of 500 mA g⁻¹ and good stability for over 100 cycles, in contrast with that of the pure-Fe₂O₃ nanoparticles which demonstrated rapid degradation to 224 mA h g⁻¹ after 50 cycles. Furthermore, the composite showed good rate capability of 280 mA h g⁻¹ at 10C (∼10,000 mA g⁻¹). These characteristics could be mainly attributed to both the use of an effective binder, poly(acrylic acid) (PAA), and the specific hybrid structures that prevent agglomeration of nanoparticles and provide buffering spaces needed for volume changes of nanoparticles during insertion/extraction of Li ions.     

Facile solvothermal synthesis of a graphene nanosheet-bismuth oxide composite and its electrochemical characteristics

This work demonstrates a novel and facile route for preparing graphene-based composites comprising of metal oxide nanoparticles and graphene. A graphene nanosheet-bismuth oxide composite as electrode materials of supercapacitors was firstly synthesized by thermally treating the graphene-bismuth composite, which was obtained through simultaneous solvothermal reduction of the colloidal dispersions of negatively charged graphene oxide sheets in N,N-dimethyl formamide (DMF) solution of bismuth cations at 180 °C. The morphology, composition, and microstructure of the composites together with pure graphite oxide, and graphene were characterized using powder X-ray diffraction (XRD), FT-IR, field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), thermogravimetry and differential thermogravimetry (TG-DTG). The electrochemical behaviors were measured by cyclic voltammogram (CV), galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS). The specific capacitance of 255 F g⁻¹ (based on composite) is obtained at a specific current of 1 A g⁻¹ as compared with 71 F g⁻¹ for pure graphene. The loaded-bismuth oxide achieves a specific capacitance as high as 757 F g⁻¹ even at 10 A g⁻¹. In addition, the graphene nanosheet-bismuth oxide composite electrode exhibits the excellent rate capability and well reversibility.