Porous carbon nanofiber (CNF) electrodes for supercapacitors were prepared by using polyacrylonitrile (PAN) and cucurbituril (CB), which is a macrocyclic compound comprising glycoluril units containing hollow cores. Mixture of PAN and CB in dimethyl sulfoxide was electrospun, and thermally treated to produce CNF electrodes. Their thermal stability, surface morphology, carbon microstructures, and surface porosity were investigated. Electrochemical properties were measured using three-electrode with synthesized CNFs without further treatment as a working electrode and 1 M Na2SO4 as an electrolyte. CNFs derived from PAN and CB exhibited a high specific capacitance of 183.5 F g− 1 and an energy density of 25.4 Wh kg− 1 at 0.5 A g− 1 with stable cyclic stability during 1000 cycles, which is significantly higher than those for CNFs derived from PAN only. This demonstrated that the introduction of CB successfully improved the energy storage performance of CNF electrodes.
Carbon nanofibers (CNFs) are promising materials for the construction of energy devices, particularly organic solar cells. In the electrospinning process, polyacrylonitrile (PAN) has been utilized to generate nanofibers, which is the simplest and most popular method of creating carbon nanofibers (CNFs) followed by carbonization. The CNFs are coated on stainless steel (SS) plates and involve an electropolymerization process. The prepared Cu, CNF, CNF–Cu, PANI, PANI–Cu, CNF–PANI, and CNF–PANI–Cu electrode materials’ electrical conductivity was evaluated using cyclic voltammetry (CV) technique in 1 M H2SO4 electrolyte solution. Compared to others, the CNF–PANI–Cu electrode has higher conductivity that range is 3.0 mA. Moreover, the PANI, CNF–PANI, and CNF–PANI–Cu are coated on FTO plates and characterized for their optical properties (absorbance, transmittance, and emission) and electrical properties (CV and Impedance) for organic solar cell application. The functional groups, and morphology-average roughness of the electrode materials found by FT–IR, XRD, XPS, SEM, and TGA exhibit a strong correlation with each other. Finally, the electrode materials that have been characterized serve to support and act as the nature of the hole transport for organic solar cells.
In this study, a milled carbon nanofiber-reinforced composite paint was prepared to enhance the anti-corrosive properties of concrete structures. Shorter-length (40 μm) milled carbon fibers (MCFs) showed an increased viscosity relative to longer MCFs (120 μm) owing to their 2 weeks (the decrease was especially strong in the acid solution). A carbon nanotube (CNT)- reinforced composite paint showed similar results in uniform distribution in the epoxy resin. The latter showed a decrease in viscosity owing to agglomerative movement in the epoxy resin. The surface hardness and tensile strength of the composite paint linearly increased as the carbon nanofiber loading was increased by up to 7.2 wt% in the epoxy resin, and slowly decreased after soaking in a sulfuric acid or sodium hydroxide solution for to those of the MCFs, whereas CNTs dispersed in isopropyl alcohol (IPA) in advance and mixed with resin showed lower hardness values than those without dispersion in IPA at the same loading. The mechanical properties such as the Shore D hardness and tensile strength of the MCF-reinforced composite paint increased significantly, resulting in a slower surface degradation of the composite paint concrete in a sulfuric acid and sodium hydroxide solution.
In this study, we have fabricated the phenolic resin (PR)/polyacrylonitrile (PAN) blend-derived core-sheath nanostructured carbon nanofibers (CNFs) via one-pot solution electrospinning. The obtained core-sheath nanostructured carbon nanofibers were further treated by mixed salt activation process to develop the activated porous CNFs (CNF-A). Compared to pure PAN-based CNFs, the activated PR/PAN blend with PR 20% (CNF28-A)-derived core-sheath nanostructured CNFs showed enhanced specific capacitance of ~ 223 F g− 1 under a three-electrode configuration. Besides, the assembled symmetric CNF28-A//CNF28-A device possessed a specific capacitance of 76.7 F g− 1 at a current density of 1 A g− 1 and exhibited good stability of 111% after 5,000 galvanostatic charge/discharge (GCD) cycles, which verifies the outstanding long-term cycle stability of the device. Moreover, the fabricated supercapacitor device delivered an energy density of 8.63 Wh kg− 1 at a power density of 450 W kg− 1.
Energy storage systems should address issues such as power fluctuations and rapid charge-discharge; to meet this requirement, CoFe2O4 (CFO) spinel nanoparticles with a suitable electrical conductivity and various redox states are synthesized and used as electrode materials for supercapacitors. In particular, CFO electrodes combined with carbon nanofibers (CNFs) can provide long-term cycling stability by fabricating binder-free three-dimensional electrodes. In this study, CFO-decorated CNFs are prepared by electrospinning and a low-cost hydrothermal method. The effects of heat treatment, such as the activation of CNFs (ACNFs) and calcination of CFO-decorated CNFs (C-CFO/ACNFs), are investigated. The C-CFO/ACNF electrode exhibits a high specific capacitance of 142.9 F/g at a scan rate of 5 mV/s and superior rate capability of 77.6% capacitance retention at a high scan rate of 500 mV/s. This electrode also achieves the lowest charge transfer resistance of 0.0063 Ω and excellent cycling stability (93.5% retention after 5,000 cycles) because of the improved ion conductivity by pathway formation and structural stability. The results of our work are expected to open a new route for manufacturing hybrid capacitor electrodes containing the C-CFO/ACNF electrode that can be easily prepared with a low-cost and simple process with enhanced electrochemical performance.
This study focused on the development of Fe–Co/kaolin catalyst by a wet impregnation method. Response surface methodology was used to study the influence of operating variables such as drying temperature, drying time, mass of support and stirring speed on the yield of the catalyst. The catalyst composite at best synthesis conditions was then calcined in an oven at varied temperature and time using 22 factorial design of experiment. The catalyst with optimum surface area was then utilized to grow carbon nanofiber (CNF) in a chemical vapour deposition (CVD) reactor. Both the catalyst and CNF were characterized using high-resolution scanning electron microscopy, high-resolution transmission electron microscopy, thermogravimetric analysis (TGA), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy. On the influence of operating variables on the yield of catalyst, the results showed that an optimum yield of 96.51% catalyst was obtained at the following operating conditions: drying time (10 h), drying temperature (110 °C), stirring speed (100 rpm) and mass of support (9 g). Statistical analysis revealed the existence of significant interactive effects of the variables on the yield of the catalyst. The HRSEM/XRD/BET/TGA analysis revealed that the particles are well dispersed on the support, with high surface area (376.5 m2/g) and thermally stable (330.88 °C). The influence of operating parameters on the yield of CNF was also investigated and the results revealed an optimum yield of 348% CNF at the following operating conditions: reaction temperature (600 °C), reaction time (40 min), argon flow rate (1416 mL/min) and acetylene/hydrogen flow rate (1416 mL/ min). It was found from statistical analysis that the reaction temperature and acetylene/hydrogen flow rates exerted significant effect on the CNF yield than the other factors. The contour and surface plots bi-factor interaction indicated functional relationship between the response and the experimental factors. The characterization results showed that the synthesized CNF is thermally stable, twisted and highly crystalline and contain surface functional groups. It can be inferred from the results of various analyses that the developed catalyst is suitable for CNF growth in a CVD reactor.
For electrodes in electrochemical double-layer capacitors, carbon nanofibers (CNFs) were prepared by thermal treatment of precursor polymer nanofibers, fabricated by electrospinning. Poly(acrylonitrile-co-vinylimidazole) (PAV) was employed as a precursor polymer of carbon nanofibers due to the effective cyclization of PAV polymer chains during thermal treatment compared to a typical precursor, polyacrylonitrile (PAN). PAV solutions with different comonomer compositions were prepared and electrospun to produce precursor nanofibers. Surface images obtained from scanning electron microscopy showed that their nanofibrous structure was well preserved after carbonization. It was also confirmed that electrospun PAV nanofibers were successfully converted to carbon nanofibers after the carbonization step by Raman spectroscopy. Carbon nanofiber electrodes derived from PAV showed higher specific capacitances and energy/power densities than those from PAN, which was tested by coin-type cells. It was also shown that PAV with an acrylonitrile/vinylimidazole composition of 83:17 is most promising for the carbon nanofiber precursor exhibiting a specific capacitance of 114 F/g. Their energy and power density are 70.1 Wh/kg at 1 A/g and 9.5 W/kg at 6 A/g, respectively. In addition, pouch cells were assembled to load the higher amount of electrode materials in the cells, and a box-like cyclic voltammetry was obtained with high capacitances.
Carbon nanofibers (CNF) are widely used as active agents for electrodes in Li-ion secondary battery cells, supercapacitors, and fuel cells. Nanoscale coatings on CNF electrodes can increase the output and lifespan of battery devices. Atomic layer deposition (ALD) can control the coating thickness at the nanoscale regardless of the shape, suitable for coating CNFs. However, because the CNF surface comprises stable C–C bonds, initiating homogeneous nuclear formation is difficult because of the lack of initial nucleation sites. This study introduces uniform nucleation site formation on CNF surfaces to promote a uniform SnO2 layer. We pretreat the CNF surface by introducing H2O or Al2O3 (trimethylaluminum + H2O) before the SnO2 ALD process to form active sites on the CNF surface. Transmission electron microscopy and energy-dispersive spectroscopy both identify the SnO2 layer morphology on the CNF. The Al2O3-pretreated sample shows a uniform SnO2 layer, while island-type SnOx layers grow sparsely on the H2Opretreated or untreated CNF.
Carbon nanofiber (CNF) is used as an electrode material for electrical double layer capacitors (EDLCs), and is being consistently researched to improve its electrochemical performance. However, CNF still faces important challenges due to the low mesopore volume, leading to a poor high-rate performance. In the present study, we prepared the unique architecture of the activated mesoporous CNF with a high specific surface area and high mesopore volume, which were successfully synthesized using PMMA as a pore-forming agent and the KOH activation. The activated mesoporous CNF was found to exhibit the high specific surface area of 703 m2 g−1, total pore volume of 0.51 cm3 g−1, average pore diameter of 2.9 nm, and high mesopore volume of 35.2 %. The activated mesoporous CNF also indicated the high specific capacitance of 143 F g−1, high-rate performance, high energy density of 17.9-13.0Wh kg−1, and excellent cycling stability. Therefore, this unique architecture with a high specific surface area and high mesopore volume provides profitable synergistic effects in terms of the increased electrical double-layer area and favorable ion diffusion at a high current density. Consequently, the activated mesoporous CNF is a promising candidate as an electrode material for high-performance EDLCs.
Ni nanoparticles (NPs)-graphitic carbon nanofiber (GCNF) composites were fabricated using an electrospinning method. The amounts of Ni precursor used as catalyst for the catalytic graphitization were controlled at 0, 2, 5, and 8 wt% to improve the photovoltaic performances of the nanoparticles and make them suitable for use as counter electrodes for dyesensitized solar cells (DSSCs). As a result, Ni NPs-GCNF composites that were fabricated with 8 wt% Ni precursors showed a high circuit voltage (0.73 V), high photocurrent density (14.26 mA/cm2), and superb power-conversion efficiency (6.72 %) when compared to those characteristics of other samples. These performance improvements can be attributed to the reduced charge transport resistance that results from the synergetic effect of the superior catalytic activity of Ni NPs and the efficient charge transfer due to the formation of GCNF with high electrical conductivity. Thus, Ni NPs-GCNF composites may be used as promising counter electrodes in DSSCs.
Ni nanoparticles (NPs)-graphitic carbon nanofiber (GCNF) composites were fabricated using an electrospinning method. The amounts of Ni precursor used as catalyst for the catalytic graphitization were controlled at 0, 2, 5, and 8 wt% to improve the photovoltaic performances of the nanoparticles and make them suitable for use as counter electrodes for dyesensitized solar cells (DSSCs). As a result, Ni NPs-GCNF composites that were fabricated with 8 wt% Ni precursors showed a high circuit voltage (0.73 V), high photocurrent density (14.26 mA/cm2), and superb power-conversion efficiency (6.72 %) when compared to those characteristics of other samples. These performance improvements can be attributed to the reduced charge transport resistance that results from the synergetic effect of the superior catalytic activity of Ni NPs and the efficient charge transfer due to the formation of GCNF with high electrical conductivity. Thus, Ni NPs-GCNF composites may be used as promising counter electrodes in DSSCs.
Octahedral Co3O4/carbon nanofiber (CNF) composites are fabricated using electrospinning and hydrothermal methods. Their morphological characteristics, chemical bonding states, and electrochemical properties are used to demonstrate the improved photovoltaic properties of the samples. Octahedral Co3O4 grown on CNFs is based on metallic Co nanoparticles acting as seeds in the CNFs, which seeds are directly related to the high performance of DSSCs. The octahedral Co3O4/CNFs composites exhibit high photocurrent density (12.73 mA/m2), superb fill factor (62.1 %), and excellent power conversion efficiency (5.61 %) compared to those characteristics of commercial Co3O4, conventional CNFs, and metallic Co-seed/CNFs. These results can be described as stemmnig from the synergistic effect of the porous and graphitized matrix formed by catalytic graphitization using the metal cobalt catalyst on CNFs, which leads to an increase in the catalytic activity for the reduction of triiodide ions. Therefore, octahedral Co3O4/CNFs composites can be used as a counter electrode for Pt-free dye-sensitized solar cells.
Carbon nanofiber (CNF) composites coated with spindle-shaped Fe2O3 nanoparticles (NPs) are fabricated by a combination of an electrospinning method and a hydrothermal method, and their morphological, structural, and chemical properties are measured by field-emission scanning electron microscopy, transmission electron microscopy, Xray diffraction, and X-ray photoelectron spectroscopy. For comparison, CNFs and spindle-shaped Fe2O3 NPs are prepared by either an electrospinning method or a hydrothermal method, respectively. Dye-sensitized solar cells (DSSCs) fabricated with the composites exhibit enhanced open circuit voltage (0.70 V), short-circuit current density (12.82 mA/cm2), fill factor (61.30%), and power conversion efficiency (5.52%) compared to those of the CNFs (0.66 V, 11.61 mA/cm2, 51.96%, and 3.97%) and spindle-shaped Fe2O3 NPs (0.67 V, 11.45 mA/cm2, 50.17%, and 3.86%). This performance improvement can be attributed to a synergistic effect of a superb catalytic reaction of spindle-shaped Fe2O3 NPs and efficient charge transfer relative to the one-dimensional nanostructure of the CNFs. Therefore, spindle-shaped Fe2O3-NPcoated CNF composites may be proposed as a potential alternative material for low-cost counter electrodes in DSSCs.
Perforated polygonal cobalt oxide (Co3O4) is synthesized using electrospinning and a hydrothermal methodfollowed by the removal of a carbon nanofiber (CNF) template. To investigate their formation mechanism, thermogravi-metric analysis, field-emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy are examined. To obtain the optimum condition of perforated polygonal Co3O4, we pre-pare three different weight ratios of the Co precursor and the CNF template: sample A (Co precursor:CNF template-10:1), sample B (Co precursor:CNF template-3.2:1), and sample C (Co precursor:CNF template-2:1). Among them, sam-ple A exhibits the perforated polygonal Co3O4 with a thin carbon layer (5.7-6.2 nm) owing to the removal of CNF tem-plate. However, sample B and sample C synthesized perforated round Co3O4 and destroyed Co3O4 powders, respectively,due to a decreased amount of Co precursor. The increased amount of the CNF template prevents the formation of polygonalCo3O4. For sample A, the optimized weight ratio of the Co precursor and CNF template may be related to the suc-cessful formation of perforated polygonal Co3O4. Thus, perforated polygonal Co3O4 can be applied to electrode materialsof energy storage devices such as lithium ion batteries, supercapacitors, and fuel cells.
WS2-W-WC embedded carbon nanofiber composites were fabricated by using electrospinning method for use in high-performance supercapacitors. In order to obtain optimum electrochemical properties for supercapacitors, WS2 nanoparticles were used as precursors and the amounts of WS2 precursors were controlled to 4 wt% (sample A) and 8 wt% (sample B). The morphological, structural, and chemical properties of all samples were investigated by means of field emission photoelectron spectroscopy, transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. These results demonstrated that the embedded phases of samples A and B were changed from WS2 to WS2-W-WC through carbothermal reaction during carbonization process. In particular, sample B presented high specific capacitance (~119.7 F/g at 5 mV/s), good high-rate capacitance (~60.5%), and superb cycleability. The enhanced electrochemical properties of sample B were explained by the synergistic effect of the using 1-D structure supports, increase of specific surface area, and improved conductivity from formation of W and WC phases.
To improve the methanol electro-oxidation in direct methanol fuel cells(DMFCs), Pt electrocatalysts embedded on porous carbon nanofibers(CNFs) were synthesized by electrospinning followed by a reduction method. To fabricate the porous CNFs, we prepared three types of porous CNFs using three different amount of a styrene-co acrylonitrile(SAN) polymer: 0.2 wt%, 0.5 wt%, and 1 wt%, respectively. A SAN polymer, which provides vacant spaces in porous CNFs, was decomposed and burn out during the carbonization. The structure and morphology of the samples were examined using field emission scanning electron microscopy and transmission electron microscopy and their surface area were measured using the Brunauer- Emmett-Teller(BET). The crystallinities and chemical compositions of the samples were examined using X-ray diffraction and X-ray photoelectron spectroscopy. The electrochemical properties on the methanol electro oxidation were characterized using cyclic voltammetry and chronoamperometry. Pt electrocatalysts embedded on porous CNFs containing 0.5 wt% SAN polymer exhibited the improved methanol oxidation and electrocatalytic stability compared to Pt/conventional CNFs and commercial Pt/ C(40 wt% Pt on Vulcan carbon, E-TEK).
Nitrogen-doped ZnO nanoparticle-carbon nanofiber composites were prepared using electrospinning. As the relative amounts of N-doped ZnO nanoparticles in the composites were controlled to levels of 3.4, 9.6, and 13.8 wt%, the morphological, structural, and chemical properties of the composites were characterized by means of field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). In particular, the carbon nanofiber composites containing 13.8 wt% N-doped ZnO nanoparticles exhibited superior catalytic properties, making them suitable for use as counter electrodes in dye-sensitized solar cells (DSSCs). This result can be attributed to the enhanced surface roughness of the composites, which offers sites for I3- ion reductions and the formation of Zn3N2 phases that facilitate electron transfer. Therefore, DSSCs fabricated with 13.8 wt% N-doped ZnO nanoparticle-carbon nanofiber composites showed high current density (16.3mA/cm2), high fill factor (57.8%), and excellent power-conversion efficiency (6.69%); at the same time, these DSSCs displayed power-conversion efficiency almost identical to that of DSSCs fabricated with a pure Pt counter electrode (6.57%).
Five vapor-grown carbon nanofiber (VGCNF) reinforced vinyl ester (VE) nanocomposite configurations were fabricated, imaged, and mechanically tested in order to obtain information on the influence and the interactions of the role of the microstructure at lower length scales on the observed continuum level properties/response. Three independent variables (the nanofiber weight fraction and two types of nanofiber mixing techniques) were chosen to be varied from low, middle, and high values at equally spaced intervals. Multiple mixing techniques were studied to gain insight into the effect of mixing on the VGCNF dispersion within the VE matrix. The point count method was used for both lower length-scale imaging techniques to provide quantitative approximations of the magnitude and the distribution of such lower length-scale features. Finally, an inverse relationship was shown to exist between the stiffness and strength properties of the resulting nanocomposites under uniaxial quasistatic compression loading.
Novel unsaturated polyester composites with PAN-based nanofiber, stabilized PAN nanofiber, and carbonized nanofiber webs have been fabricated, respectively, and the effects of the nanofiber web content on their electrical resistivity, the thermal stability, dynamic storage modulus, and fracture surfaces were studied. The result demonstrated that the introduction of just one single layer (which is corresponding to 2 wt.%) of the carbonized nanofiber web to unsaturated polyester resin (UPE) could contribute to reducing markedly the electrical resistivity of the resin reflecting the percolation threshold, to improving the storage modulus, and to increasing the thermal stability above 350℃. The effect on decreasing the resistivity and increasing the modulus was the greatest at the carbonized PAN nanofiber web content of 8 wt.%, particularly showing that the storage modulus was increased about 257~283% in the measuring temperature range of -25℃ to 50℃. The result also exhibited that the carbonized PAN nanofibers were distributed uniformly and compactly in the unsaturated polyester, connecting the matrix three-dimensionally through the thickness direction of each specimen. It seemed that such the fiber distribution played a role in reducing the electrical resistivity as well as in improving the dynamic storage modulus.
Nanostructured carbon materials have been found to have applications in fuel cell electrodes, field emitters, electronic devices, sensors and electromagnetic absorbers, etc. Especially, the CNF (carbon nanofiber) can be expected to play an important role in catalyst supporters for fuel cell electrodes and chemical reactions. In this study, we synthesized CNF from a liquid phase carbon source by a solvothermal method. In addition, we studied the parameters for the preparation of CNF by controlling heating and cooling rates, synthesis temperature and time. We characterized the CNF by SEM/TEM, XRD, Raman spectroscopy and EDS. We found that the heating and cooling rate have strong effects on the CNF formation and growth. We were able to prepare the best CNF at the heating rate of 10˚/min, at 450˚ for 60 minutes, and at the cooling rate of 4˚/min. As a result of Raman spectra, we found that the sample showed two characteristic Raman bands at ~1350cm-1 (D band) and ~1600cm-1 (G band). The G band indicates the original graphite feature, but the D band has been explained as a disorder feature of the carbon structure. The diameter and length of the CNF was about 15~20nm, and over 1μ, respectively.