Exponential growth of electrochemical double layer capacitance in glassy carbon during thermal oxidation

The evolution of the electrochemical double layer capacitance of glassy carbon during thermochemical gas phase oxidation was studied with electrochemical impedance spectroscopy. Particular attention was paid to the initial oxidation stage, during which the capacitance grows exponentially. This stage could be experimentally assessed by lowering the reaction temperature and oxidant partial pressure. After a specific oxidation time the capacitance growth experiences a cross-over to a logistic growth.     

Superior electric double layer capacitors using ordered mesoporous carbons

This paper reports for the first time superior electric double layer capacitive properties of ordered mesoporous carbon (OMCs) with varying ordered pore symmetries and mesopore structure. Compared to commercially used activated carbon electrode, Maxsorb, these OMC carbons have superior capacitive behavior, power output and high-frequency performance in EDLCs due to the unique structure of their mesopore network, which is more favorable for fast ionic transport than the pore networks in disordered microporous carbons. As evidenced by N₂ sorption, cyclic voltammetry and frequency response measurements, OMC carbons with large mesopores, and especially with 2-D pore symmetry, show superior capacitive behaviors (exhibiting a high capacitance of over 180 F/g even at very high sweep rate of 50 mV/s, as compared to much reduced capacitance of 73 F/g for Maxsorb at the same sweep rate). OMC carbons can provide much higher power density while still maintaining good energy density. OMC carbons demonstrate excellent high-frequency performances due to its higher surface area in pores larger than 3 nm. Such ordered mesoporous carbons (OMCs) offer a great potential in EDLC capacitors, particularly for applications where high power output and good high-frequency capacitive performances are required.     

Capacitance limits of high surface area activated carbons for double layer capacitors

A large specific surface area (SSA) of carbon materials used for electrochemical double layer capacitors (EDLC) is the most important parameter leading to a large gravimetric capacitance (C_g). However, for a SSA determined with the differential functional theory (DFT) model above a value of 1200 m²/g the plot of C_g versus S_DFT exhibits a plateau. We suggest that this limitation of C_g can be ascribed to a space constriction for charge accommodation inside the pore walls. As a consequence, the use of extremely high surface area carbons for EDLCs may be unprofitable.     

A novel method for carbon modification with minute polyaniline deposition to enhance the capacitance of porous carbon electrodes

A novel method was developed for minute deposition of polyaniline onto microporous activated carbon fabric to enhance the capacitance of the carbon serving as electrodes for electrochemical capacitors. The deposition consisted of pre-adsorption of monomer into carbon micropores followed by electrochemical polymerization of the adsorbed monomer in a monomer-free H₂SO₄ solution at 0.85 V vs. Ag/AgCl. In comparison with the conventional polymerization in a monomer solution, the developed deposition resulted in a polymer framework distributed over the vast surface in carbon micropores, thus leading to a lower resistance for ion binding with the polymer in H₂SO₄ during charge-discharge. The lower resistance gave rise to a higher specific capacitance for the deposited polymer. In the assembled two-electrode capacitors, the usage of polyaniline redox reactions to store charges was more prominent for polymer-carbon composite electrodes from the developed method because of the higher electrode open circuit potentials. The present work has demonstrated that a capacitance enhancement of >50% in comparison with bare carbon can be achieved with minute polyaniline deposition (<5 wt.%) using the developed method, while only 22% was reached using the conventional method.     

Preparation and pore control of highly mesoporous carbon from defluorinated PTFE

Porous carbon having more than 2000 m²/g of BET specific surface area was synthesized by defluorination of polytetrafluoroethylene (PTFE) at 473 K using sodium metal. The porous carbon as-prepared had a large amount of narrow mesopores 2-3 nm in pore width, together with micropores. Control of the pore structure was attempted by simple heat-treatment of the carbon in nitrogen, and change of the porous structures was characterized by nitrogen adsorption techniques. As a result, it was found that the ratio between micro- and mesopores was easily varied. Electric double layer capacitance was measured as one of the applications for the mesoporous carbon with specific porosity, and the effect of pore control on capacitance was investigated.     

Templated pyrolytic carbon: the effect of poly(ethylene glycol) molecular weight on the pore size distribution of poly(furfuryl alcohol)-derived carbon

Poly(ethylene glycol), which has a negligible carbon yield upon pyrolysis, was used as a template to study the controlled formation of mesoporosity in pyrolytic carbons. A series of carbons was produced from mixtures of poly(ethylene glycol) and poly(furfuryl alcohol) with 25, 50 and 75% composition by weight and an M_n of 300 to18?500 g/mol of template. Polydisperse dextran adsorption reveals a maximum in uptake for 8000 g/mol and 50% templated carbons, while materials from 75% mixtures or those from less than 2000 g/mol template yielded negligible dextran uptake. These results correlated well with the intensity ratio of a broad peak between 7 and 11° 2θ in the X-ray diffraction spectrum and the 002 diffraction peak and also qualitatively with micrographs of the internal microstructure of the carbons. The results suggest a templating process dominated by both the molecular size of the template and the rate of expulsion of decomposed template material during the formation of the solid.     

Highly mesoporous carbonaceous material of activated carbon beads for electric double layer capacitor

The activated carbon beads (ACB) are prepared by a new preparation method, which is proposed by mixing the coal tar pitch and fumed silica powder at a certain weight ratio and activation by KOH at different weight ratios and different temperatures. The BET surface area, pore volume and average pore size are obtained based on the nitrogen adsorption isotherms at 77 K by using ASAP 2010 apparatus. The results show that our samples have much high specific surface area (SSA) of 3537 m² g⁻¹and high pore volume value of 3.05 cm³ g⁻¹. The percentage of mesopore volume increases with the weight ratio of KOH/ACB ranging from 4% to 72%. The electrochemical double layer capacitors (EDLCs) are assembled with resultant carbon electrode and electrolyte of 1 mol L⁻¹ Et₄NBF₄/PC. The specific capacitance of the ACB sample could be as high as 191.7 F g⁻¹ by constant current charge/discharge technique, indicating that the ACB presents good characteristics prepared by the method proposed in this work. The investigation of influence of carbon porosity structure on capacitance indicates that the SSA plays an important role on the capacitance and all the pore sizes of less than 1 nm, from 1 to 2 nm and larger than 2 nm contribute to the capacitance. Mesopore structure is beneficial for the performance at high current density.     

Radial distribution of porosity in spherical activated carbon particles

The radial distribution of porosity in spherical activated carbon particles and its relationship to both activation temperature and conversion of the reaction C-CO₂ are discussed. Char spheres, obtained by pelletizing Quercus agrifolia powdered char, were activated using CO₂ as activating agent at 820 and 860 °C. For both temperatures, the gasification reaction was run until the desired conversion (30, 50 and 70%) was reached. The activation process was performed using TGA apparatus. The porosity of the samples was measured by physical adsorption of nitrogen at −196 °C. BET and Dubinin-Raduskhevich equations were used to analyse the results. From each activated carbon sphere several samples were prepared, corresponding to different layers of the sphere; an outer layer, a middle layer and the core of the particle. From these results, the radial porosity evolution as a function of activation temperature and reaction conversion was obtained and a mathematical expression that correlates pore volume evolution and reaction conversion is proposed.     

Kinetics of pyrolytic carbon infiltration for the preparation of ceramic/carbon and carbon/carbon composites

Carbon/carbon and zeolite/carbon composites have been prepared by pyrolytic carbon infiltration of organic and inorganic substrates with different porous structures. The chemical vapour infiltration kinetics of these substrates has been studied in a thermogravimetric system at atmospheric pressure, using benzene as pyrolytic carbon precursor. The rate of pyrolytic carbon infiltration seems to depend on the porosity of the substrate available to the pyrolytic carbon precursor, irrespective of the nature of the substrate studied. Activation energy values of about 180 kJ/mol were found for the different substrates used in the temperature range of 700-800 °C, where the cracking reaction of benzene takes place, predominantly, in a heterogeneous form. At higher temperatures homogeneous reactions compete with heterogeneous ones and higher values of activation energies (280-380 kJ/mol) were obtained. The oxidation of the pyrolytic carbon deposited on the different substrates studied takes place in the same range of temperature, which suggests the presence of a similar pyrolytic carbon structure on substrates of different nature or a similar accessibility to the deposited layer.     

Influence of oxygen treatment on electric double-layer capacitance of activated carbon fabrics

Oxygen treatment at 250°C on polyacrylonitrile-based activated carbon fabric was conducted to explore the influence of carbon-oxygen complexes on the performance of capacitors fabricated with the carbon fabric. Surface analysis showed that most of the oxygen functional groups created from the oxygen treatment were the carbonyl or quinone type. The performance of the capacitors was tested in 1 M H₂SO₄, using potential sweep cyclic voltammetry and constant current charge-discharge cycling. It was found that the Faradaic current, the contributor of pseudocapacitance, increased significantly with the extent of oxygen treatment, while the increase in the double-layer capacitance was minor. Due to the treatment the overall specific capacitance showed an increase up to 25% (e.g., from 120 to 150 F g⁻¹ at a current density of 0.5 mA cm⁻²). However, the distributed capacitance effect, the inner resistance and the leakage current were found to increase with the extent of oxidation. It is suggested that due to the local changes of charge density and the increase in redox activity the presence of the carbonyl- or quinone-type functional groups may induce double-layer formation, Faradaic current, surface polarity, and electrolyte decomposition.     

Influence of pore structure and surface chemistry on electric double layer capacitance in non-aqueous electrolyte

The performance as electric double layer capacitors (EDLC) in non-aqueous electrolyte of a series of alkaline agent-activated carbons with high surface area is presented in this work. The results obtained show that, in general, capacitance increases with surface area. However, the results obtained in this study confirm that capacitance not only depends on surface area, but also on two other parameters: pore size distribution and surface chemistry. It has been shown that capacitance is higher for a sample with wider micropore size distribution than for a sample with higher surface area but too narrow micropore size distribution. In addition, it has been observed that the sample with a very high amount of surface groups presents very high capacitance values. In the present study, a KOH-activated carbon with a capacitance as high as 220 F/g was prepared. Finally, the results obtained with a mesoporous sample have shown that the presence of mesopores in activated carbons with very high surface area (e.g. >2000 m²/g), do not seem to be effective for double layer capacitors.     

The effect of silica template structure on the pore structure of mesoporous carbons

We have synthesized two kinds of mesoporous carbons using a spherical silica sol (SMC1 carbon) and an elongated silica sol (SMC3 carbon) as templates. Nitrogen isotherms and electrochemical experiments were performed to investigate the effect of the silica template structure on the pore structure of the resulting mesoporous carbons. When carbons produced using the same silica to resorcinol molar ratio were compared, both nitrogen isotherms and electrochemical studies revealed that the SMC3 carbons exhibit simpler pore connectivity than SMC1 carbons.     

Preparation of porous carbons from thermoplastic precursors and their performance for electric double layer capacitors

Porous carbons with high surface area were successfully prepared from thermoplastic precursors, such as poly(vinyl alcohol) (PVA), hydroxyl propyl cellulose and poly(ethylene terephthalate), by the carbonization of a mixture with MgO at 900 °C in an inert atmosphere. After carbonization the MgO was dissolved out using a diluted sulfuric acid and the carbons formed were isolated. The mixing of the PVA carbon precursor with the MgO precursors (reagent grade MgO, magnesium acetate or citrate) was done either in powder form or in an aqueous solution. The BET surface area of the carbons obtained via solution mixing could reach a very high value, such as 2000 m²/g, without any activation process. The pore structure of the resultant carbons was found to depend strongly on the mixing method; the carbons prepared via solution mixing were rich in mesopores, but those produced via powder mixing were rich in micropores. The size of mesopores was found to be almost the same as that of the MgO particles, suggesting a way of controlling the mesopore size in the resultant carbons. Measurement of capacitance was carried out in 1 mol/L H₂SO₄ electrolyte. The porous carbon with a BET surface area of 1900 m²/g prepared at 900 °C through solution mixing of Mg acetate with PVA showed a fairly high EDLC capacitance, about 250 F/g with a current density of 20 mA/g and 210 F/g with 1000 mA/g. The rate performance was closely related to the mesoporous surface area.     

Preparation of fibrous porous materials by chemical activation 2. H3PO4 activation of polymer coated fibers

Fibrous porous materials (FPMs) have been prepared by coating a glass fiber with an aqueous solution of poly(vinyl alcohol) (PVA) and H₃PO₄, followed by stabilization and heat treatment in air. The H₃PO₄ was then removed by washing with deionised water and NaOH. The results show that H₃PO₄ acts as a dehydration agent to promote pyrolytic and thermal crosslinking of PVA at a much lower temperature of 170 °C, leading to FPMs having much higher char yields and surface areas. The activation in air is of benefit to achieve higher surface areas as compared to using N₂. Utilizing a fiberglass mat to support coatings of PVA activated with H₃PO₄ results in much higher specific surface areas. The activation temperature, activation time and concentration of H₃PO₄ have strong effects on the surface area, pore size distribution and coating content of FPMs.     

Effect of oxygen functional groups on synthetic carbons on liquid phase oxidation of cyclohexanone

Synthetic carbons from phenolic resins were used as catalysts for the aqueous phase oxidation of cyclohexanone to C₄-C₆ dicarboxylic acids (adipic, glutaric and succinic acids) at 413 K under 50 bar total air pressure. The changes in microporous structure and surface chemistry, produced as a consequence of activation or heat treatment processes, were analyzed. Using CO₂ or air as activating agent increased significantly the surface area and the total pore volume responsible for the activity. The surface chemistry of the samples was also modified and was characterized by titration with bases of different strength and with HCl, by temperature programmed desorption, and by X-ray photoelectron spectroscopy. To determine the role of surface oxygen functionalities on the catalytic behavior of the carbons, heat treatments in nitrogen at different temperatures were used to selectively eliminate oxygenated groups. Thus, treatment at temperatures of 1173 K eliminating the carbonyl/quinone groups decreased the selectivity to adipic acid and dicarboxylic acids. Introducing quinone groups during the synthesis of the carbons also improved the selectivity to adipic acid, proving that the mechanism of oxidation involves the quinone type groups on the carbon surface.