Composites of olive-like manganese oxalate on graphene sheets for supercapacitor electrodes

MnC₂O₄/graphene composites are prepared by a facile hydrothermal reaction with KMnO₄ using ascorbic acid as a reducing agent. Olive-like MnC₂O₄ particles are distributed uniformly on the surface of graphene sheets. The composites are evaluated as supercapacitor electrodes, which show that the specific capacitance of MnC₂O₄/graphene composites is 122 F g^?1, more than twice as high as that of free MnC₂O₄ at a current density of 0.5 A g^?1. In addition, this composite material exhibits an excellent cycle stability with the capacitance retention of 94.3 % after 1,000 cycles.     

Reduced graphene oxide/MWCNT hybrid sandwiched film by self-assembly for high performance supercapacitor electrodes

A reduced graphene oxide/multiwalled carbon nanotube (RGO/MWCNT) hybrid sandwiched film with different MWCNTs content was prepared by vacuum-assisted self-assembly from a complex dispersion of graphene oxide (GO) and MWCNTs followed by heat-treating at 200 °C for 1 h in a vacuum oven to reduce the GO into RGO. The free-standing RGO/MWCNT hybrid sandwiched film before heat-treatment showed a layered structure with an entangled network of MWCNTs sandwiched between the GO sheets. This unique structure not merely contribute to remove the oxygen-containing groups in GO during the heat-treatment, but also decrease the defects for electron transfer between RGO layers, which enhances the electrochemical capacitive performances of graphene-based films. A specific capacitance up to 379 F/g was achieved based on RGO/MWCNT with 30 % MWCNTs mass fraction at 0.1 A/g in a 6 M KOH electrolyte. The excellent performance of RGO/MWCNT hybrid sandwiched film signifies the importance of controlling the surface chemistry and sandwiched nanostructure of graphene-based materials.     

Hierarchical porous nitrogen-doped partial graphitized carbon monoliths for supercapacitor

Porous carbon monoliths have attracted great interest in many fields due to their easy availability, large specific surface area, desirable electronic conductivity, and tunable pore structure. In this work, hierarchical porous nitrogen-doped partial graphitized carbon monoliths (N–MC–Fe) with ordered mesoporous have been successfully synthesized by using resorcinol-formaldehyde as precursors, iron salts as catalyst, and mixed triblock copolymers as templates via a one-step hydrothermal method. In the reactant system, hexamethylenetetramine (HMT) is used as nitrogen source and one of the carbon precursors under hydrothermal conditions instead of using toxic formaldehyde. The N–MC–Fe show hierarchically porous structures, with interconnected macroporous and ordered hexagonally arranged mesoporous. Nitrogen element is in situ doped into carbon through decomposition of HMT. Iron catalyst is helpful to improve the graphitization degree and pore volume of N–MC–Fe. The synthesis strategy is user-friendly, cost-effective, and can be easily scaled up for production. As supercapacitors, the N–MC–Fe show good capacity with high specific capacitance and good electrochemical stability.

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Graphical abstract Hierarchical porous nitrogen-doped partial graphitized carbon monoliths with ordered mesoporous have been successfully synthesized by using resorcinol-formaldehyde as precursors, iron as catalyst, and mixed triblock copolymers as templates via a one-step hydrothermal method.

     

Hollow polypyrrole nanosphere embedded in nitrogen-doped graphene layers to obtain a three-dimensional nanostructure as electrode material for electrochemical supercapacitor

A novel approach was developed to prepare hollow polypyrrole (PPy) nanospheres and nitrogen-doped graphene/hollow PPy nanospheres (NG/H-PPy) composites. In this process, uniform poly (methyl methacrylate-butyl methacrylate-methacrylic acid) (PMMA-PBMA-PMAA) latex microspheres as sacrificial templates were synthesized by using an emulsion polymerization method. Then, hollow PPy nanospheres were obtained on the surface of PMMA-PBMA-PMAA microspheres by in situ chemical oxidative polymerization. Finally, H-PPy was embedded in NG layers successfully through a simple approach. The nanobeads have been characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectra, and Fourier transform infrared spectra (FTIR). Different electrochemical methods including cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), and electrochemical impedance spectroscopy (EIS) have been applied to study the electrochemical properties. The specific capacitance of NG/H-PPy composites based on the three-electrode system is as high as 575 F g^?1 at a current density of 1 A g^?1 and enhanced stability about 90.1 % after 500 cycles, indicating that the composite has an impressive capacitance and excellent cycling performance.     

Fabrication of ionic polymer actuator with graphene nanocomposite electrodes and its characterization

In the present study, a novel ionic polymer actuator employing a graphene nanocomposite (GN) as its electrodes was fabricated. By a conventional solvent mixing of a graphene nanopowder and polystyrene, a GN solution was prepared. The solution was then utilized in a dip coating process of an ionic polymer membrane, forming a thin liquid GN layer on the surfaces of the ionic polymer membrane. After removing the solvent from the coated film, the solidified conducting GN layer could be obtained, which was used as the electrodes in the ionic polymer actuator. An electrical property of the GN layer formed by the present method was characterized, confirming the possibility of the present GN in the actuator applications. Simple and reverse bending motions of the fabricated actuator were also investigated, verifying the usefulness of both the GN layer and the present simple fabrication method.     

Three-dimensional nitrogen-doped graphene/sulfur composite for lithium-sulfur battery

A three-dimensional nitrogen-doped graphene/sulfur composite (NGS3) was synthesized by a simple hydrothermal method using urea as the nitrogen source and subsequent thermal treatment. The structure and electrochemical performance of the prepared nitrogen-doped graphene/sulfur composite (NGS3) were confirmed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), Energy dispersive spectroscopy mapping (EDS), and galvanostatic charge/discharge measurements. SEM and EDS mapping show that NGS3 exhibits a porous structure with uniform distribution of sulfur. Compared with the graphene/sulfur composite (NGS1), NGS3 delivers an outstanding rate capability with 1501, 1278, 1136, and 1024 mAh g^?1 at 200, 400, 800, and 1000 mA g^?1, respectively, and the cycle stability of NGS3 is also wonderful, a reversible discharge capacity of 1330 mAh g^?1 is obtained after 80 cycles under the current rate of 200 mA g^?1. The wonderful electrochemical performance could be attributed to the special three-dimensional conductive structure with the help of nitrogen atom.     

Thermal properties of triangle nitrogen-doped graphene nanoribbons

We investigate the thermal properties of triangle nitrogen-doped graphene nanoribbons (TNGNs) with different nitrogen-doped concentrations (0.11% to 2.31%) at different temperatures ($200\text{K}～600\text{K}$) using non-equilibrium molecular dynamics. The results show that the nitrogen atoms doped at the edge of the defect can increase the thermal conductivity of graphene nanoribbons, but with the increase of the nitrogen-doped concentrations from 0.11% to 2.31%, the thermal conductivity decreases sharply. In addition, nitrogen atoms reduces the sensitivity of the thermal conductivity to temperature. Besides, the thermal rectification is found, and it increases with the raise of nitrogen-doped concentration. Finally, in order to verify the correctness of the thermal rectification, we calculate the phonon power spectra of TNGNs with nitrogen-doped concentrations of 0.11% and 2.31% at 300 K. These research has important reference value for the control of heat in microelectronic devices.     

Synthesis and electronic structure of nitrogen-doped graphene

The crystalline and electronic structure of nitrogen-doped graphene (N-graphene) has been studied by photoelectron spectroscopy and scanning tunneling microscopy. Synthesis of N-graphene from triazine molecules on Ni(111) surface results in incorporation into graphene of nitrogen atoms primarily in the pyridinic configuration. It has been found that inclusions of nitrogen enhance significantly thermal stability of graphene on nickel. An analysis of the electronic structure of N-graphene intercalated by gold atoms has revealed that the pyridinic nitrogen culminates in weak p-type doping, in full agreement with theoretical predictions. Subsequent thermal treatment makes possible conversion of the major part of nitrogen atoms into the substitutional configuration, which involves n-type doping. It has been shown that the crystalline structure of the N graphene thus obtained reveals local distortions presumably caused by inhomogeneous distribution of impurities in the layer. The results obtained have demonstrated a promising application potential of this approach for development of electronic devices based on graphene with controllable type of conduction and carrier concentration.     

Modulating magnetism of nitrogen-doped zigzag graphene nanoribbons

We present a study of electronic properties of zigzag graphene nanoribbons （ZGNRs） substitutionally doped with nitrogen atoms at a single edge by first principle calculations. We find that the two edge states near the Fermi level sepa- rate due to the asymmetric nitrogen-doping. The ground states of these systems become ferromagnetic because the local magnetic moments along the undoped edges remain and those along the doped edges are suppressed. By controlling the charge-doping level, the magnetic moments of the whole ribbons are modulated. Proper charge doping leads to interest- ing half-metallic and single-edge conducting ribbons which would be helpful for designing graphene-nanoribbon-based spintronic devices in the future.     

CVD synthesis of nitrogen-doped graphene using urea

This work provides an effective low-cost synthesis and in-depth mechanistic study of high quality large-area nitrogen-doped graphene(NG) films. These films were synthesized using urea as nitrogen source and methane as carbon source, and were characterized by scanning electron microscopy(SEM), Raman spectroscopy and X-ray photoelectron spectroscopy(XPS). The N doping level was determined to be 3.72 at.%, and N atoms were suggested to mainly incorporated in a pyrrolic N configuration. All distinct Raman peaks display a shift due to the nitrogen-doping and compressive strain. The increase in urea concentration broadens the D and 2D peak's Full Width at Half Maximum(FWHM), due to the decrease of mean free path of phonons. The N-doped graphene exhibited an n-type doping behavior with a considerably high carrier mobility of about 74.1 cm2/(V s), confirmed by electrical transport measurements.     

Fabrication of bimetallic Pt/Pd nanoparticles on 2-thiolbenzimidazole functionalized reduced graphene oxide for methanol oxidation

In this study, an electrocatalyst based on 2-thiolbenzimidazole (TBI) functionalized reduced graphene oxide (rGO) with platinum and palladium nanoparticles (Pt-PdNPs) was synthesized. The successful synthesis of nanomaterials and the prepared glassy carbon electrode (GCE) surfaces were confirmed by transmission electron microscope, X-ray photo electron spectroscopy, scanning electron microscope, electrochemical impedance spectroscopy and X-ray diffraction method. The effective surface areas of TBIrGO/GCE, PdNPs/TBIrGO/GCE, PtNPs/TBIrGO/GCE and Pt-PdNPs/TBIrGO/GCE were calculated to be 324, 578, 667 and 1189 cm²/mg, respectively. According to the results, the electrochemical surface area of the Pt-PdNPs/TBIrGO is 3.67, 2.06 and 1.78 times higher than those of TBIrGO, PdNPs/TBIrGO and PtNPs/TBIrGO, respectively. The Pt-PdNPs/TBIrGO/GCE also exhibited higher peak current for methanol oxidation than those of comparable TBIrGO/GCE, PdNPs/TBIrGO/GCE, PtNPs/TBIrGO/GCE modified GCEs, thus providing evidence for its higher electro-catalytic activity.     

Graphene oxide with improved electrical conductivity for supercapacitor electrodes

Predominant few-layer graphene (FLG) sheets of high electrical conductivity have been synthesized by a multi-step intercalation and reduction method. The electrical conductivity of the as-synthesized FLG is measured to be ∼3.2 × 10⁴ S m⁻¹, comparable to that of pristine graphite. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman analysis reveal that the as-synthesized FLG sheets have large areas with single and double layers. The specific capacitance of 180 F g⁻¹ is obtained for the FLG in a 1 M Na₂SO₄ aqueous electrolyte by integrating the cyclic voltammogram. The good capacitive behavior of the FLG is very promising for the application for next-generation high-performance electrochemical supercapacitors.     

Galvanostatically deposited Fe: MnO2 electrodes for supercapacitor application

The present investigation describes the addition of iron (Fe) in order to improve the supercapacitive properties of MnO₂ electrodes using galvanostatic mode. These amorphous worm like Fe: MnO₂ electrodes are characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDAX), Fourier transform infrared spectroscopy (FTIR) and wettability test. The supercapacitive properties of MnO₂ and Fe: MnO₂ electrodes are investigated using cyclic voltammetry, chronopotentiometry and impedance techniques. It is seen that the supercapacitance increases with increase in Fe doping concentration and achieved a maximum of 173 F g^?1 at 2 at% Fe doping. The maximum supercapacitance obtained is 218 F g^?1 for 2 at% Fe: MnO₂ electrode. This hydrous binary oxide exhibited ideal capacitive behavior with high reversibility and high pulse charge–discharge property between ?0.1 and +0.9 V/SCE in 1 M Na₂SO₄ electrolyte indicating a promising electrode material for electrochemical supercapacitors.     

Zn-Co oxide electrodes with excellent capacitive behavior for using supercapacitor application

In the present study, super-capacitive behavior of spinel Zn-Co oxides (with different Zn⁺²/Co⁺² mol ratio) has been thoroughly investigated. The spinel of transition metal oxides with different morphologies has been synthesized with hydrothermal method on Ni foam as substrate layer. The specific capacitance of the Zn-Co oxide electrode prepared at 180 °C for 5 h with different Zn⁺²/Co⁺² mol ratios of 1:0, 2:1, 1:1, 1:2, 0:1 were investigated and measured 405, 842, 726, 1237, 705 F g^?1, respectively at 50 mV s^?1 scan rate. Zn-Co oxide with Zn⁺²/Co⁺² mol ratio of 1:2 was also synthesized at two different temperatures of 120 and 150 °C for 5 h with the specific capacitance of 1147, 917 F g^?1 at 50 mV s^?1 scan rate, respectively. Among the obtained data, the sample with Zn⁺²/Co⁺² mol ratio of 1:2 prepared at 180 °C for 5 h possessed highest specific capacitance. The cyclic life of this electrode showed 92% capacitance retention after 1000 cycle of charge-discharge. All results revealed that Zn-Co oxides had excellent supercapacitive properties due to multiple oxidation states and fast ion/electron transfer at the surface of electrode which could be offered as suitable devices for energy storage applications.     

First-principle study of nanostructures of functionalized graphene

We present first-principle calculations of 2D nanostructures of graphene functionalized with hydrogen and fluorine, respectively, in chair conformation. The partial density of states, band structure, binding energy and transverse displacement of C atoms due to functionalization (buckling) have been calculated within the framework of density functional theory as implemented in the SIESTA code. The variation in band gap and binding energy per add atom have been plotted against the number of add atoms, as the number of add atoms are incremented one by one. In all, 37 nanostructures with 18C atoms, 3 × 3 × 1 (i.e., the unit cell is repeated three times along x-axis and three times along y-axis) supercell, have been studied. The variation in C–C, C–H and C–F bond lengths and transverse displacement of C atoms (due to increase in add atoms) have been tabulated. A large amount of buckling is observed in the carbon lattice, 0.0053–0.7487 Å, due to hydrogenation and 0.0002–0.5379 Å, due to fluorination. As the number of add atoms (hydrogen or fluorine) is increased, a variation in the band gap is observed around the Fermi energy, resulting in change in behaviour of nanostructure from conductor to semiconductor/insulator. The binding energy per add atom increases with the increase in the number of add atoms. The nanostructures with 18C+18H and 18C+18F have maximum band gap of 4.98 eV and 3.64 eV, respectively, and binding energy per add atom –3.7562 eV and –3.3507 eV, respectively. Thus, these nanostructures are stable and are wide band-gap semiconductors, whereas the nanostructures with 18C+2H, 18C+4H, 18C+4F, 18C+8F, 18C+10F and 18C+10H atoms are small band-gap semiconductors with the band gap lying between 0.14 eV and 1.72 eV. Fluorine being more electronegative than hydrogen, the impact of electronegativity on band gap, binding energy and bond length is visible. It is also clear that it is possible to tune the electronic properties of functionalized graphene, which makes it a suitable material in microelectronics.     

Synthesis and characterization of nitrogen-doped graphene hollow spheres as electrode material for supercapacitors

Recently, the rapid development of graphene industry in the world, especially in China, provides more opportunities for the further extension of the application field of graphene-based materials. Graphene has also been considered as a promising candidate for use in supercapacitors. Here, nitrogen-doped graphene hollow spheres (NGHS) have been successfully synthesized by using industrialized and pre-processed graphene oxide (GO) as raw material, SiO₂ spheres as hard templates, and urea as reducing-doping agents. The results demonstrate that the content and pretreatment of GO sheets have important effect on the uniform spherical morphologies of the obtained samples. Industrialized GO and low-cost urea are used to prepare graphene hollow spheres, which can be a promising route to achieve mass production of NGHS. The obtained NGHS have a cavity of about 270 nm, specific surface area of 402.9 m² g^?1, ultrathin porous shells of 2.8 nm, and nitrogen content of 6.9 at.%. As electrode material for supercapacitors, the NGHS exhibit a specific capacitance of 159 F g^?1 at a current density of 1 A g^?1 in 6 M KOH aqueous electrolyte. Moreover, the NGHS exhibit superior cycling stability with 99.24% capacitive retention after 5000 charge/discharge cycles at a current density of 5 A g^?1.     

Polyaniline-Containing composites based on highly porous carbon cloth for flexible supercapacitor electrodes

Composites based on commercially available carbon cloth Busofit T-040 and conductive polymer polyaniline are fabricated using the electrochemical polymerization of aniline on the surface of carbon-cloth fibers. The sequence of technological operations for obtaining the composite is optimized; the procedure of preliminary modification of the carbon-cloth surface by electrochemical etching is worked out; and the capacitive characteristics of the obtained composites for use as flexible supercapacitor electrodes are studied. It is found that the introduction of polyaniline into the composition of composite electrode structures leads to an increase in the capacitance by 2–2.5 times compared to the initial carbon cloth due to the pseudocapacitance of polyaniline while maintaining a high electrical conductivity and efficiency. For a composite based on etched carbon cloth, the specific capacitance is 267 F/g (8.9 F/cm² per unit of the geometric surface of the electrode) with a charge efficiency of 97–99%. The specific surface area of the composite, determined by the BET method, is 548 m²/g.     

Highly concentrated, stable nitrogen-doped graphene for supercapacitors: Simultaneous doping and reduction

In this work, we developed a concentrated ammonia-assisted hydrothermal method to obtain N-doped graphene sheets by simultaneous N-doping and reduction of graphene oxide (GO) sheets. The effects of hydrothermal temperature on the surface chemistry and the structure of N-doped graphene sheets were also investigated. X-ray photoelectron spectroscopy (XPS) study of N-doped graphene reveals that the highest doping level of 7.2% N is achieved at 180 °C for 12 h. N binding configurations of sample consist of pyridine N, quaternary N, and pyridine-N oxides. N doping is accompanied by the reduction of GO with decreases in oxygen levels from 34.8% in GO down to 8.5% in that of N-doped graphene. Meanwhile, the sample exhibits excellent N-doped thermal stability. Electrical measurements demonstrate that products have higher capacitive performance than that of pure graphene, the maximum specific capacitance of 144.6 F/g can be obtained which ascribe the pseudocapacitive effect from the N-doping. The samples also show excellent long-term cycle stability of capacitive performance.     

Studies on the performances of silica aerogel electrodes for the application of supercapacitor

Silica aerogel (SiO₂ aerogel) was prepared by sol–gel method from tetraethyl orthosilicate hydrolyzation and has been characterized by scanning electron microscopy and N₂ adsorption for its surface structure, surface area, and pore-size distribution. Constant current charge–discharge technique, cyclic voltammetry, and electrochemical impedance spectrum were employed for its specific capacitance and equivalent series resistance. The results showed that the maximum specific capacitance of SiO₂ aerogel electrode in 1 M Et₄NBF₄/PC electrolyte was 62.5 F g⁻¹. In addition, the SiO₂ aerogel capacitor exhibits excellent long-term stability with no significant degradation after 500 charging and discharging cycles. Therefore, the application of high surface area SiO₂ aerogel as electrodes in supercapacitor devices is promising.     

Hydrothermal synthesis of carbon- and reduced graphene oxide-supported CoMoO4 nanorods for supercapacitor

Hybrid CoMoO₄ nanorods with carbon (C) and graphene oxide (rGO) are successfully synthesized via one-step hydrothermal process. Hybrid α-CoMoO₄ nanorods have shown excellent electrochemical performances compared to pristine CoMoO₄ in alkaline electrolyte. Specifically, CoMoO₄/C nanorod exhibits a maximum specific capacitance of 451.6 F g^?1 at the current density of 1 A g^?1, whereas CoMoO₄/rGO shows high specific capacitance of 336.1 F g^?1 at the same current density. Both the hybrid nanorods show good rate capability even at high current density of 20 A g^?1 and long-term cyclic stability. The observed electrochemical features of the hybrid CoMoO₄ nanostructure could be attributed to the presence of highly conductive carbonaceous material on unique one-dimensional nanorod microstructure which enhances the electrical conductivity of the nanorods thereby allowing faster electrolyte ion diffusion during the redox process.