Pore characteristics and electrochemical performance of ordered mesoporous carbons for electric double-layer capacitors

Three types of ordered mesoporous carbon materials with different pore characteristics have been synthesized via different routes. Whatever the synthesis route was, triblock copolymer was employed as both a carbon precursor and a structure-directing agent. The relationship between the capacitances of carbon electrodes and their pore characteristics was elucidated in detail. The material C-P exhibits the lowest resistance and highest specific capacitance value of exceeding 170 F/g among these carbon materials, which can be due to not only high surface area but also its appropriate pore size distribution. In addition, the noteworthy is that the maintenance of specific capacitance with increasing current load for each sample is better than that for general activated carbons, where larger mesopores and high mesopore fraction play important roles in the rate capability.     

KOH activation of ordered mesoporous carbons prepared by a soft-templating method and their enhanced electrochemical properties

Ordered mesoporous carbon (COU-2) was synthesized by a soft-templating method. The COU-2 mesoporous carbon was activated by using KOH to improve its porosity. The mesopore size of COU-2 was 5.5 nm and did not change by the KOH activation. But, the BET surface area of COU-2 largely increased from 694 to 1685 m²/g and total pore volume was increased from 0.54 to 0.94 cm³/g after the KOH activation. The large increase of micropore volume is due to the increase of the surface area. Electrochemical cyclic voltammetry measurements were conducted in aqueous (1 M sulfuric acid) and organic (1 M tetraethyl ammonium tetrafluoroborate/polypropylene carbonate) electrolyte solutions. The KOH-activated COU-2 carbon shows superior capacitances over the COU-2 carbon and a commercial microporous carbon both in aqueous and organic electrolyte solutions. These results suggest that the carbons having regularly-interconnected uniform mesopores and micropores in thin pore walls are desirable for the electrodes in electrochemical double-layer capacitors.     

Simple hydrothermal synthesis of ordered mesoporous carbons from resorcinol and hexamine

Hexamine has been used as a release source of formaldehyde towards the self-assembly synthesis of resorcinol/formaldehyde (RF) resin-based mesoporous carbons under hydrothermal conditions. The obtained mesoporous carbons exhibit the micrometer-sized, sphere-like morphology and a high surface area. The use of hexamine instead of formaldehyde efficiently harnesses the organic–organic self-assembly of RF resin and block copolymer. Ordered mesostructures can be obtained over a wide range of hydrothermal temperature without the extra addition of inorganic bases or acids as catalysts. The method described here has the advantage of being a one-pot procedure and only involves the use of several organic precursors in an aqueous system.     

Surface chemistry of ordered mesoporous carbons

Ordered mesoporous carbons (OMC) were produced by pyrolysis of hydrocarbons adsorbed in two different silica matrices (MCM-48 and SBA-15), followed by dissolution of the matrix in either hydrofluoric acid or sodium hydroxide. Some carbons were subsequently heat treated at temperatures of up to 1600 °C. The chemistry of the external surface was studied by X-ray photoelectron spectroscopy (XPS) and static secondary ion mass spectroscopy (SIMS). Information on the graphitic order of the surface of the mesopores was obtained from low-pressure nitrogen adsorption data. The external and internal surface of the OMC has a polyaromatic, graphite-like character. This character increases considerably with increasing pyrolysis and/or post-pyrolysis temperature, as expected. According to the XPS and the nitrogen adsorption data, this increase was especially pronounced for temperatures above 1100 °C. In spite of the different pore structures, only small differences in the polyaromatic character were found for OMC synthesised either in a MCM-48 or in a SBA-15 matrix. Differences exist for the non-carbon elements. When hydrofluoric acid is used for dissolution of the silica matrix, organic fluorine compounds are formed. Their concentration is higher when a MCM-48 matrix as opposed to a SBA-15 matrix was used. Dissolution of the silica matrix in sodium hydroxide yielded a less contaminated OMC as compared to dissolution in hydrofluoric acid.     

Synthesis of nanocast ordered mesoporous carbons and their application as electrode materials for supercapacitor

Various nanocast ordered mesoporous carbons (OMCs) were synthesized using mesoporous silicas such as SBA-15, SBA-16, KIT-6, SBA-3 and MCM-48 as templates via nanocasting pathway. The structures of OMCs were analyzed by X-ray diffraction, transmission electron microscope and nitrogen sorption technique. These OMCs with well-defined pore structure were used as model electrode materials for investigating the influence of pore structure on their double layer capacitances. The cyclic voltammetry and galvanostatic charge/discharge measurements were conducted to estimate the capacitive behaviour of OMCs. The results show that the mesopore structures of OMCs play an important role in improving surface utilization for the formation of electrical double layer. OMCs synthesized from SBA-15 and SBA-16 show great advantage over others because their micropores are being easy accessible through the mesopores, thus allowing rapid electrolyte ion diffusion. To achieve a higher specific capacitance (μF cm⁻²), the optimized amount ratio between micropore and mesopore needs to be controlled. In addition, great impact of the electrode disc thickness on the capacitive performance was demonstrated by a series of careful measurements.     

Avoiding structure degradation during activation of ordered mesoporous carbons

Hierarchical micro–mesoporous carbons with high porosity development and ordered structure were prepared. The innovative proposal consists in developing microporosity in ordered mesoporous carbon by chemical activation in template presence in order to minimize the structural damage. Thus, we have directly carried out the chemical activation of a mesoporous carbon/silica composite with KOH. The effect on mesoporous ordered structure of both KOH/carbon ratio and activation temperature has been studied. Following chemical activation the specific surface area is increased from 341 to 1757 m²/g and the micropore volume becomes almost six times larger than initial value. Although a slight widening of the mesopore distribution and an increase in the mesopore volume has been observed during activation, TEM and XRD results reveal an excellent conservation of the ordered mesoporous structure during activation even at conditions well above the limits that a CMK-3 type carbon can resist.     

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.     

Comparative study on the electrocatalytic activities of ordered mesoporous carbons and graphene

In this work, a comparative study on the electrocatalytic activities of ordered mesoporous carbons (OMCs) and graphene (GR) is presented. Using voltammetry and amperometry as detection methods, four DNA bases, double-stranded DNA (dsDNA), six important electroactive compounds and various biomolecules were employed to investigate their electrochemical responses on OMC and GR modified glassy carbon electrodes (OMC/GCE and GR/GCE). The results show that OMC/GCE enhances the electron transfer kinetics of these compounds compared to GR/GCE. The discrepancy in electrochemical activities can be attributed to the different microstructures of OMC and GR, which were examined by transmission electron microscopy, X-ray photoelectron spectra, X-ray diffraction, Raman spectra and nitrogen adsorption–desorption.     

分级多孔炭的制备及其电化学性能研究

以间苯二酚和甲醛为前驱体,原位合成的Mg(OH)2为模板剂,KOH作为催化剂、沉淀剂、活化剂,一步法合成具有小/中/大孔的分级多孔炭。使用扫描电镜、透射电镜、氮气吸附、X射线衍射对样品的结构进行表征。通过恒流充放电、循环伏安、电化学阻抗谱,测试样品在1mol/L的(C2H5)4NBF4/碳酸丙烯酯(Propylene carbonatePC)电解液中的电化学性能。结果表明,随着KOH对间苯二酚用量的增加,材料的比表面积和孔容先增大后减小,其最大值分别为1300m2/g和0.89cm3/g。该材料具有良好的容量性能和功率性能,在电流密度0.1A/g时,最高质量比电容可以达到116F/g;当电流密度增大到5A/g时,电容保持率为78%。     

Templating synthesis of ordered mesoporous carbon particles

This research reports the synthesis of spherical ordered mesoporous carbon particles using mesoporous silica particles as a template. The silica particles with ordered cubic and lamellar mesostructures were synthesized from an aerosol-assisted self-assembly process using block copolymer surfactants as the structural directing agent. Infiltrating the pores of the silica particles with a sucrose solution followed by carbonization, and silica removal results in mesoporous carbon particles with replicated mesostructures. The particles were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and nitrogen sorption techniques.     

Ni- and CuNi-modified activated carbons and ordered mesoporous CMK-3 for furfural hydrotreatment

In this paper, various carbon materials such as activated carbons and mesoporous carbon material CMK-3 modified with nickel and copper, are investigated in the production of a potential biofuel 2-methylfuran with furfural hydrotreatment. Deep characterization of the prepared catalysts revealed differences in pore size, surface area, and metal particle size. Furthermore, the acidity of the catalysts varied significantly affecting the product distribution. Very high activity and selectivity towards 2-methylfuran was achieved with two steam activated carbons (Norit RB4C and Darco) and ordered mesoporous carbon material CMK-3 modified with copper and nickel. 2-Methylfuran yield as high as 60.2% was achieved with 5/5 wt% CuNi/RB4C in 2 h at 230 °C. The operation in slurry phase was observed to promote the reaction towards 2-methylfuran.