Hierarchical porous carbons with controlled micropores and mesopores for supercapacitor electrode materials

Various porous carbons were prepared by CO₂ activation of ordered mesoporous carbons and used as electrode materials for supercapacitor. The structures were characterized by using X-ray diffraction, transmission electron microscopy and nitrogen sorption at 77 K. The effects of CO₂ treatment on their pore structures were discussed. Compared to the pristine mesoporous carbons, the samples subjected to CO₂ treatment exhibited remarkable improvement in textural properties. The electrochemical measurement in 6 M KOH electrolyte showed that CO₂ activation leads to better capacitive performances. The carbon CS15A6, which was obtained after CO₂ treatment for 6 h at 950 °C using CMK-3 as the precursor, showed the best electrochemical behavior with a specific gravimetric capacitance of 223 F/g and volumetric capacitance of 54 F/cm³ at a scan rate of 2 mV/s and 73% retained ratio at 50 mV/s. The good capacitive behavior of CS15A6 may be attributed to the hierarchical pore structure (abundant micropores and interconnected mesopores with the size of 3-4 nm), high surface area (2749 m²/g), large pore volume (2.09 cm³/g), as well as well-balanced microporosity and mesoporosity.     

The effect of SiC substrate microstructure and impurities on the phase formation in carbide-derived carbon

Carbon layers were obtained by etching of different silicon carbides with Cl₂/H₂ gas mixtures at high temperatures (carbide-derived carbon). The resulting layers were studied by analytical and high resolution transmission electron microscopy. It was found, that etching of high purity single crystal SiC wafers exclusively yields amorphous carbon. The development of graphite-like and nanodiamond inclusions was observed using commercially available sintered SiC and polymer-derived SiC, which both contained boron- and carbon-rich phases. The presence of turbostratic graphite regions and isolated diamond particles in the bulk of non-chlorinated sample was revealed in the commercial polycrystalline SiC substrate. This fact points to the possible nucleation and growth of diamond phases during sintering of the commercial SiC substrate. Chlorination of boron-implanted single crystal SiC wafer showed that the presence of boron-rich dopants in the SiC alone does not trigger the nucleation of diamond phases. An initial surplus of carbon in the SiC substrates appeared to be required as could be shown for boron doped polycarbosilane derived SiC. Thermodynamic considerations assisted by quantum chemical calculations showed the low effect of hydrogen in the Cl₂/H₂ gas mixtures during SiC chlorination for the nucleation of diamond phases.     

Influence of the acid concentration on the morphology of micropores and mesopores in porous glasses

The polymodal microporosity and mesoporosity of porous glasses prepared by through leaching of phase-separated alkali borosilicate glasses in hydrochloric acid solutions of different concentrations are investigated by two new methods based on an analysis of the kinetic and equilibrium isotherms of gas desorption at a temperature of 77.5 K under low partial pressures, as well as by a modified classical adsorption method under medium and high pressures. It is established that an increase in the concentration of hydrochloric acid in the leaching solution brings about transformations in the microporous and mesoporous structures of the porous glasses. The structural transformations can be summarized as follows: (i) a considerable decrease in the specific surface of mesopores and the corresponding increase in the diameter of secondary silica globules, (ii) a decrease in the mesopore volume and the corresponding increase in the coordination number of the packing of secondary silica globules in channels formed upon phase separation, (iii) an increase in the diameter of mesopores arising from gaps between secondary silica globules in channels formed upon phase separation, (iv) an increase in the diameter of regions in these channels that are partially or completely free from secondary silica globules, and (v) the formation of ultramicropores with a molecular size of 0.4–0.5 nm.     

In-situ thermal activation of carbide-derived carbon

Microporous carbons attract high interest due to their application as a medium for gas storage, catalyst support or electrode material in lithium ion batteries or supercapacitors. Carbide-derived carbons (CDC) produced by halogenation of carbides exhibit a narrow pore size distribution and a tunable pore and microstructure by choosing the appropriate carbide precursor and chlorination temperature. However, the pore volume is limited by the amount of metal in the carbide structure, and the variation of pore size by varying the process conditions is not possible for all carbides. With an in-situ thermal activation in CO₂ parallel to the chlorination, the porosity of the CDC materials can be further increased. This improved carbide-derived carbon process also allows producing novel pore structures which vary in the meso- to micropore ratio from the outside to the center of the particle. Thereby also the boarder case of shell-like carbon structures showing different pore size distributions in the shells can be produced. For this in-situ activation and chlorination of carbides the influence of the processing, the concentration of CO₂ and activation time on the pore structure of CDC was studied.     

碳化物衍生碳及其在吸附领域中的应用研究进展

碳化物衍生碳（CDC）是近年来开发的一种具有纳米结构的新型多孔碳材料。该材料是将碳化物前体通过物理（如热分解等）或化学（如卤化等）过程,由表及里逐层刻蚀掉非碳原子得到的,可以实现原子水平上的调控。本文介绍了CDC的制备工艺、性质（孔和形貌）及其在吸附领域中的应用。结果表明,可以通过控制刻蚀温度、碳化物前体、后处理等合成条件实现CDC比表面积大范围可调、孔径及孔径分布等微观结构精确可控,得到从无定形碳到高度有序的石墨、碳纳米管或石墨烯等多种结构。最后指出了解制备过程-结构-性质之间的关系有利于精确调控CDC以满足特定应用的要求。     

Slow diffusion of methane in ultra-micropores of silicon carbide-derived carbon

We investigate macroscopic uptake kinetics of CH₄ in silicon carbide-derived carbon (SiC-DC). Ultra-microprosity in SiC-DC is found based on CO₂ adsorption at 273 K, but which has poor accessibility to Ar at 87 K. The adsorption kinetics of CH₄ is found to follow a bidisperse pore structure model, considering relatively rapid particle scale diffusion in large micropores, and a much slower local grain (or microparticle) scale diffusion in ultra-micropores. The grain scale activation energies are comparable with values for carbon molecular sieves, and consistent with values expected for the size range of the ultra-micropores, while the activation energies for transport in the larger particle scale micropores are comparable to those for conventional activated carbons. The particle scale diffusivities compare well with the results of equilibrium molecular dynamics simulations using a hybrid reverse Monte Carlo simulation constructed model of SiC-DC, with similar activation energy. On the other hand microscopic quasi-elastic neutron scattering measurements are found to probe only short-range barriers with lower activation energy. It is anticipated that ultra-micropores will not make a significant contribution to the transport in any membrane or adsorption-based process based on SiC-DC, due to the extremely slow transport in these ultra-micropores and their small pore volume.     

Electrical double-layer characteristics of novel carbide-derived carbon materials

A variety of nanoporous carbide-derived carbon materials possessing improved pore size distributions were synthesised from a mixture of titanium carbide and titanium dioxide. It was observed that TiO₂ caused partial oxidation of the carbon particles created during high-temperature chlorination of the TiC/TiO₂ mixture. The resulting carbon powder is characterised by narrow pore size distribution with a peak pore size of around 8 Å and a noticeably smaller amount of pores below 6-7 Å compared to the carbon derived from pure TiC. Electrochemical and electrical double-layer characteristics of novel carbon materials in the acetonitrile solution of triethylmethylammonium tetrafluoroborate were obtained by using cyclic voltammetry and constant current methods. Carbon electrode materials of this study were tested over the temperature range from −10 °C to +60 °C. Results of this study affirmed a great potential of the synthesised advanced carbide-derived carbon, whose specific double-layer capacitance reaches approximately 90 F cm⁻³ and 125 F g⁻¹.     

Properties of electrolytes in the micropores of activated carbon

The dependence of the composition of aqueous electrolytes in the pore system of activated carbon on the potential has been determined by monitoring the amount of ions exchanged with the external electrolyte upon immersion and upon changing the electrode potential. From the investigation with KF solutions, a quantity δ/√? = 4 × 10⁻¹⁰ m is evaluated where δ is half the width of the micropores, and ? the (relative) permittivity. This is in accordance with δ ≈ 1 nm and ? ≈ 7 applying to essentially immobilized water and fits into the results with the other electrolytes. Anions are adsorbed in the cases of sodium perchlorate and potassium hydroxide, while protons are adsorbed in the case of acids (HCl, H₂SO₄). The adsorption of ClO₄⁻ seems to result from electrostatic interaction with the solid, while H⁺ and OH⁻ are strongly chemisorbed, probably at surface groups like >CO. Ionic mobilities of ions in the micropores have been determined from conductance measurements concerning the pore electrolyte of a single spherical particle of activated carbon. Mobilities are more than one order of magnitude lower than those in bulk electrolyte, probably due to an increased viscosity of the liquid in the narrow pores and/or to the coulombic interaction with charged domains of the solid. The rate of charging of the capacitor (solid/micropore electrolyte) is assisted by macropores distributing ions throughout the carbon material.     

Nanostructured carbide-derived carbon synthesized by chlorination of tungsten carbide

Nanostructured carbide-derived carbons were synthesized from α-tungsten carbide (WC-CDC) powder via gas phase chlorination within the temperature range from 700 to 1100 °C. Analysis of X-ray diffraction results showed that WC-CDC are mainly amorphous consisting of relatively small graphitic crystallites and the apparent crystallite size along the a- and c-directions of graphite structure L_a ≈ 4 nm and L_c ≈ 1.5 nm were calculated. The first-order Raman spectra showed the graphite-like absorption peak at ∼1590 cm⁻¹ and the disorder-induced peak at ∼1350 cm⁻¹. The low-temperature N₂ sorption experiments were performed and a specific micropore surface area up to 1550 m² g⁻¹ and total pore volume up to 0.89 cm³ g⁻¹ were obtained for WC-CDC synthesized at T = 1100 °C. High-resolution transmission electron microscopy and electron energy loss spectroscopy studies revealed that WC-CDC prepared at 800 °C correspond to the highly disordered carbon material but WC-CDC prepared at 1100 °C showed partial graphitization.     

中孔煤基磁性活性炭的制备及性能表征

为提高活性炭的回收性能,以褐煤为原料,Fe3O4为赋磁剂,采用一步法制备了中孔煤基磁性活性炭,并通过低温氮气吸附、X射线衍射光谱(XRD)和振动样品磁强计(VSM)对磁性活性炭的比表面积、孔隙结构、赋磁剂晶型、磁性能进行表征,研究了炭化和活化条件对磁性活性炭性能的影响。结果表明,Fe3O4不仅能催化炭烧蚀,而且能赋予活性炭磁性,最终以生成的Fe O、γ-Fe2O3和未反应的Fe3O4形式分散在磁性活性炭内。在Fe3O4添加量6%,炭化温度650℃,炭化60 min,活化温度930℃,活化时间120 min,水蒸气流量0.77 g/(g·h)的优化工艺条件下,煤基磁性中孔活性炭的比表面积达到370 m2/g,中孔率达到55.7%,比饱和磁化强度1.36 emu/g,剩磁0.46 emu/g,矫顽力643.17Oe,比磁化率7.19×10-6m3/kg。该煤基磁性活性炭属弱磁性矿物类,可采用强磁选机进行磁选回收。     

碳化物衍生碳的制备及其在气体存储与超级电容器领域的应用研究进展

介绍了二元碳化物与三元碳化物作为前体制备碳化物衍生碳,概述了碳化物衍生碳的几种常见命名,详细阐述了管式炉中氯气高温刻蚀碳化物、多孔化碳材料的制备工艺过程和原理,总结了碳化物衍生碳孔径结构及应用,并着重介绍了在储氢储甲烷和超级电容器电极材料两方面的应用研究。碳化物衍生碳材料的甲烷吸附存储量可以达到18.5%（质量分数）,氢的吸附存储量达到6.2%（质量分数）,作为超级电容器电极材料,它的质量比电容是120F/g,且具有非常高的体积比电容（90F/cm3）,在MEMS等小型化微电子器件中有重要的应用。最后展望了这种新型碳材料通过调控微观结构与改善性能在更多领域的重要应用。     

Synthesis and characterisation of nanoporous carbide-derived carbon by chlorination of vanadium carbide

Nanoporous carbide-derived carbon (CDC) was synthesised from vanadium carbide (VC) powder via gas phase chlorination in the temperature range from 500 to 1100 °C. The XRD analysis of nanoporous carbon powder samples was carried out to investigate the structural changes (graphitisation) of nanoporous carbons synthesised. The first-order Raman spectra showed the absorption peak at ∼1582 cm⁻¹ and the disorder-induced (D) peak at ∼1345 cm⁻¹. The low-temperature N₂ adsorption experiments were performed and a specific surface area up to 1305 m² g⁻¹ and total pore volume up to 0.66 cm³ g⁻¹ were obtained.     

Adsorption and desorption of small molecule volatile organic compounds over carbide-derived carbon

Carbide-derived carbon (CDC) was prepared by selective extraction of titanium from titanium carbide in a flow of freshly prepared chlorine. The dynamic adsorption and desorption performance of CDC of small molecule volatile organic compounds (VOCs) including methanol, acetaldehyde and acetone, was investigated and compared with that of two types of commercial activated carbons. The physicochemical properties of carbons were characterized by nitrogen adsorption, temperature programmed desorption, Raman spectroscopy and transmission electron microscopy. It was observed that the CDC could adsorb much more VOCs than commercial activated carbons (especially for the less polar methanol). The desorption behavior of VOCs from the saturated CDC was similar to that of commercial activated carbons, with adsorbed VOCs desorbed in the maximum degree at 110–150 °C, which indicated that the adsorption sites for the VOCs on the three carbon adsorbents were similar and the saturated CDC could be effectively regenerated by simple heat treatment just like commercial activated carbons. Based on the characterizations, the large adsorption capacity of CDC was attributed to its larger micropore volume, narrower pore distributions (0.7–1.5 nm), as well as higher specific surface area than those of two commercial activated carbons.     

Synthesis of nanoporous carbide-derived carbon by chlorination of titanium silicon carbide

Synthesis of nanoporous carbide-derived carbon, CDC, by extraction of titanium and silicon from Ti₃SiC₂ by chlorine is discussed in this work. Thermodynamic simulations using a Gibbs free energy minimization program provided general guidelines to the experimental design. Raman spectroscopy, X-ray diffraction, and electron microscopy studies showed that the structure of CDC depends on the chlorination temperature. The low temperature synthesis resulted in an amorphous CDC structure. Noticeable graphite formation starts above 800 °C and well ordered graphite ribbons of 1-3 nm in thickness form at 1200 °C. The macroscopic volume and shape of Ti₃SiC₂ preform were preserved during the transformation. However, the chlorination resulted in the formation of cracks between the former grains of the polycrystalline Ti₃SiC₂ preform. These cracks are believed to be caused by a contraction in the direction perpendicular to the basal planes of Ti₃SiC₂. The synthesized nanoporous carbon demonstrated excellent sorption properties. Energy dispersive X-ray spectroscopy studies showed that Ti₃SiC₂ material chlorinated at 400 °C is capable of trapping over 40 wt.% of Cl₂.     

Effect of transition metal catalysts on the microstructure of carbide-derived carbon

Carbon materials with different microstructure can be produced by a carbide-derived carbon (CDC) approach varying the carbide precursor and the reaction conditions for the selective etching of the metal. CDC was produced using biomorphic TiC and SiC ceramics derived from paper preforms by a chemical vapor infiltration and reaction technique. In this work the effect of transition metal salt catalysts such as Ru(III), Fe(II), Fe(III) or Ru(III)/Fe(III) on the chlorination process at temperatures in the range 600-1200 °C as well as on the microstructure of the resulting carbon was investigated. The produced CDC was characterized by its degree of order and pore structure using Raman spectroscopy, high resolution transmission electron microscopy and low temperature nitrogen adsorption. A higher etching rate as well as a higher degree of order at lower reaction temperatures was observed if a catalytically active metal was present during the chlorination process. This effect was mostly pronounced in the case of a Ru(III)/Fe(III) bimetallic catalyst. The higher degree of order of the carbon is associated with an increased amount of mesopores and with a decrease in specific surface area. Therefore, the CDC processing in the presence of catalysts offers another way to produce ordered carbon structures at lower temperatures.     

Impact of carbon nanotube additives on carbide-derived carbon-based electroactive polymer actuators

The effects of single-walled carbon nanotubes (SWCNTs) on the properties of carbide-derived carbon (CDC)-based electroactive polymer (EAP) actuators were studied. SWCNTs were used as an additive to increase the mesoporosity and electrical conductivity of the electrodes, and also to support the CDC matrix. EAP actuators with various ratios of SWCNTs to CDC in the electrodes were fabricated and their electromechanical and electrochemical characteristics were examined. The addition of SWCNTs to CDC-based electrodes significantly increased the bending strain and stress (bending force) of the actuators. The actuator assembled with electrodes containing SWCNTs and CDC in the ratio 50/50 (wt.%/wt.%) showed the highest strain output among the samples at lower frequencies (<0.1 Hz). The increase in maximum strain was more than twice that of pure CDC-based EAPs (0.85% vs. 0.35% at an applied voltage of ±2 V). Also, the high frequency (5–50 Hz) response of the combined SWCNT/CDC-based actuators was considerably improved.