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.     

New carbon materials with high porosity in the 1-7 nm range obtained by chemical activation with phosphoric acid of resorcinol-formaldehyde aerogels

Chemical activation of resorcinol-formaldehyde aerogels with phosphoric acid results in materials containing both intra-particle microporosity (pore volume ∼0.18 cm³g⁻¹ and mean-pore-width ∼1 nm) and inter-particle micro/mesoporosity. The latter forms as a result of partial collapse of the mesopore structure of the organic aerogel and can be controlled by varying the phosphoric acid/organic aerogel ratio. Increasing this ratio leads to higher pore volume and size and it was possible to obtain micro/mesopore volumes as high as 1.23 cm³g⁻¹ with pore widths up to ∼7 nm. Over 90% of these pores were accessible even after blocking all of the ultramicroporosity by pre-adsorption of n-nonane.     

Nanoscale fine-tuning of porosity of carbide-derived carbon prepared from molybdenum carbide

Micro- and mesoporous carbide-derived carbon (CDC) was synthesised from molybdenum carbide (Mo₂C) powder by gas phase chlorination in the temperature range from 400 to 1200 °C. Analysis of XRD results show that C(Mo₂C), chlorinated at 1200 °C, consist mainly on graphitic crystallites of mean size, L_a = 9 nm and L_c = 7.5 nm. The first-order Raman spectra showed the graphite-like absorption peak at ∼1587 cm⁻¹ and the disorder-induced (D) peak at ∼1348 cm⁻¹. The low-temperature N₂ adsorption experiments were performed and a specific surface area up to 1855 m² g⁻¹ and total pore volume up to 1.399 cm³ g⁻¹ were obtained. Sorption measurements showed the presence of both micro- and mesopores after chlorination at 400-900 °C and only mesopores after chlorination at 1000°-1200 °C. Stepwise formation of micro- and mesopores was achieved and the peak pore size can be shifted from 0.8 nm up to 4 nm by increasing the chlorination temperature.     

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.     

Characterisation of activated nanoporous carbon for supercapacitor electrode materials

Commercial nanoporous carbon RP-20 was activated with water vapor in the temperature range from 950 °C to 1150 °C. The XRD analysis was carried out on nanoporous carbon powder samples to investigate the structural changes (graphitisation) in modified carbon that occurred at activation temperatures T ? 1150 °C. The first-order Raman spectra showed the absorption peak at 1582 cm⁻¹ and the disorder (D) peak at 1350 cm⁻¹. The low-temperature N₂ adsorption experiments were performed at −196 °C and a specific surface area up to 2240 m²g⁻¹ for carbon activated at T = 1050 °C was measured. The cell capacitance for two electrode activated nanoporous carbon system advanced up to 60 F g⁻¹ giving the specific capacitance ∼240 F g⁻¹ to one electrode nanoporous carbon ∣1.2 M (C₂H₅)₃CH₃NBF₄ + acetonitrile solution interface. A very wide region of ideal polarisability for two electrode system (∼3.2 V) was achieved. The low frequency limiting specific capacitance very weakly increases with the rise of specific area explained by the mass transfer limitations in the nanoporous carbon electrodes. The electrochemical characteristics obtained show that some of these materials under discussion can be used for compilation of high energy density and power density non-aqueous electrolyte supercapacitors with higher power densities than aqueous supercapacitors.     

Metal-organic framework (MOF) as a template for syntheses of nanoporous carbons as electrode materials for supercapacitor

Five nanoporous carbons (NPCs) were prepared by polymerizing and then carbonizing carbon precursor of furfuryl alcohol accommodated in a porous metal-organic framework (MOF-5, [Zn₄O(bdc)₃], bdc = 1,4-benzenedicarboxylate) template. The Brunauer-Emmett-Teller (BET) surface areas for five NPC samples obtained by carbonizing at the temperatures from 530 to 1000 °C fall into the range from 1140 to 3040 m² g⁻¹ and the dependence of BET surface areas on carbonization temperatures shows a “V” shape. All the five NPC samples have a pore size distribution centered at about 3.9 nm. As electrode materials for supercapacitor, the NPC samples obtained at the temperatures higher than 600 °C display the ideal capacitor behaviors and give rise to almost constant specific capacitance (above 100 F g⁻¹ at 5 mV s⁻¹) at various sweep rates, which is associated with their mesoporous characteristics. However, the NPC sample with the highest BET surface area (3040 m² g⁻¹) obtained by carbonizing at 530 °C gives a unusually low capacitance (12 F g⁻¹ at 5 mV s⁻¹), which may be attributed to the poor conductivity of the carbon material due to the low carbonization temperature.     

Polypyrrole/carbon composite electrode for high-power electrochemical capacitors

Nano-thin polypyrrole (PPy) layers with thickness from ∼5 nm to several 10s nm were deposited on vapor grown carbon fibers (VGCF) by an in situ chemical polymerization. Using different concentrations of the pyrrole could control the thicknesses of deposited PPy layers. Surface morphology and thickness of the deposited PPy layers were confirmed by means of scanning electron microscopy and scanning transmission emission microscopy. Pseudo-capacitive behavior of the deposited PPy layers on VGCF investigated by means of cyclic voltammetry. Then, the PPy/VGCF composites were mixed with activated carbons (AC) at various mixing ratios. For the PPy/VGCF/AC composite electrodes, characteristics of specific capacitance and power capability were examined by half-cell tests. As results of this study, it was investigated that nano-thin PPy layer below ∼10 nm deposited on VGCF had high pseudo-capacitance and fast reversibility. Its specific capacitance per averaged weight of active material (PPy) was obtained as ∼588 F g⁻¹ at 30 mV s⁻¹ and maintained as ∼550 F g⁻¹ at 200 mV s⁻¹ of scan rate. Also, from the mixing 60 wt.% of the PPy/VGCF with 25 wt.% of AC, the PPy/VGCF/AC composite electrode exhibited higher power capability maintaining the specific capacitance per active materials of PPy and AC as ∼300 F g⁻¹ at 200 mV s⁻¹ in 6 M KOH.     

Influence of oxidation process on the adsorption capacity of activated carbons from lignocellulosic precursors

A set of activated carbon materials non-oxidised and oxidised, were successfully prepared from two different lignocellulosic precursors, almond shell and vine shoot, by physical activation with carbon dioxide and posterior oxidation with nitric acid. All samples were characterised in relation to their structural properties and chemical composition, by different techniques, namely nitrogen adsorption at 77 K, elemental analysis (C, H, N, O and S), point of zero charge (PZC) and FTIR. A judicious choice was made to obtain carbon materials with similar structural properties (apparent BET surface area ∼ 850-950 m²g⁻¹, micropore volume ∼ 0.4 cm³g⁻¹, mean pore width ∼ 1.2 nm and external surface area ∼ 14-26 m²g⁻¹). After their characterisation, these microporous activated carbons were also tested for the adsorption of phenolic compounds (p-nitrophenol and phenol) in the liquid phase at room temperature. The performance in liquid phase was correlated with their structural and chemical properties. The oxidation had a major impact at a chemical level but only a moderate modification of the porous structure of the samples. The Langmuir and Freundlich equations were applied to the experimental adsorption isotherms of phenolic compounds with good agreement for the different estimated parameters.     

Synthesis of nanosized vanadium pentoxide/carbon composites by spray pyrolysis for electrochemical capacitor application

Nanostructured vanadium pentoxide/carbon (V₂O₅/carbon) composite powders with enhanced specific capacitance were synthesized by the spray pyrolysis technique. Electrochemical properties were examined by the cyclic voltammetry technique. Following analysis of powders sprayed at different temperatures, composite powders obtained at an optimum temperature of 450 °C yielded a maximum specific capacitance of 295 F g⁻¹ in 2 M KCl electrolyte at a 5-mV s⁻¹ scan rate. The weight percentage of carbon-related species was 2.7 wt% in this V₂O₅/carbon composite, as detected by thermogravimetric analysis (TGA) and confirmed by transmission electron microscope energy dispersive spectroscopy (TEM-EDS) analysis. Following initial X-ray diffraction (XRD) characterization, scanning electron microscope (SEM), TEM and high-resolution TEM (HRTEM) imaging revealed a specific morphology of spherical shell agglomerates of V₂O₅ nanorods and nanoribbons, with each shell comprising a network of these one- and two-dimensional nanoparticles in an amorphous carbon matrix. The V₂O₅ network was not fully dense, and the majority of the nanorod sizes were in the range of 50-150 nm, with additional long nanoribbons extending from the outsides of the spherical shells. The specific surface area was 18 m² g⁻¹ for the composite powders, and the pore size distribution revealed that the majority of pores had diameters in the range of 40-50 Å, which was relatively larger than the pore diameters obtained at 500 °C and would be beneficial for electrochemical performance. The enhancement of the specific capacitance in V₂O₅/carbon composites was attributed to the distribution of amorphous carbon throughout the V₂O₅ and the particular open nanostructure.     

The effect of Mo2C derived carbon pore size on the electrical double-layer characteristics in propylene carbonate-based electrolyte

Carbide-derived carbon (CDC) was synthesised from molybdenum carbide by extracting Mo atoms in a high-temperature chlorine atmosphere. A systematic study of the influence of pore size on the electrical double layer (EDL) performance was carried out with carbons synthesised in the temperature interval of 500-900 °C. Strong effect of chlorination conditions on the pore-size distribution was noticed that gives wide possibilities to vary the pore structure of Mo₂C derived carbons. An average pore size of carbons varied between 1 nm and 2 nm depending on chlorination temperature. The relationships were established between the pore-size distribution and the electrochemical performance of micro/mesoporous carbons. The EDL characteristics of carbon materials in a propylene carbonate solution of triethylmethylammonium tetrafluoroborate were obtained using the cyclic voltammetry at ΔE of 3.8 V and the constant current methods in a 3-electrode test cell. A novel test method was developed to demonstrate the power characteristics of the electrode materials. The results of this study affirmed the great potential of Mo₂C derived carbons, whose EDL capacitance reaches ∼65 F cm⁻³ and 132 F g⁻¹ and the 20-s discharge power density is 2.1 W cm⁻³.     

Energy and power performance of electrochemical double-layer capacitors based on molybdenum carbide derived carbon

Cyclic voltammetry, constant current charge/discharge, and electrochemical impedance spectroscopy have been applied to establish the electrochemical characteristics for electric double-layer capacitor (EDLC) consisting of the 1 M (C₂H₅)₃CH₃NBF₄ electrolyte in acetonitrile and micro/mesoporous carbon electrodes prepared from Mo₂C, noted as C(Mo₂C). The N₂ sorption (total BET specific surface area (S_BET ≤ 1855 m² g⁻¹), micropore area (S_micro ≤ 1823 m² g⁻¹), total pore volume (V_tot ≤ 1.399 m³ g⁻¹) and pore size distribution (average NLDFT pore width d_NLDFT ≥ 0.89 nm) values obtained have been correlated with the electrochemical characteristics for EDLCs (region of ideal polarizability (ΔV = 3.0 V), characteristic time constant (τ_R = 1.05 s), gravimetric capacitance (C_m ≤ 143 F g⁻¹)) dependent strongly on the C(Mo₂C) synthesis temperature. High gravimetric energy (35 Wh kg⁻¹) and gravimetric power (237 kW kg⁻¹) values, normalised to the total active mass of both C(Mo₂C) electrodes, synthesised at T_synt = 800 °C, have been demonstrated at cell voltage 3.0 V and T = 20 °C.     

Relationship between pore surface areas and electric double layer capacitance in non-aqueous electrolytes for air-oxidized carbon spheres

To investigate the relationship between pore structure and specific capacitance of electric double layer capacitors with non-aqueous electrolytes, phenol resin based carbon spheres were modified by oxidation in dry air, giving a wide range of pore structure. Surface area due to the presence of different pores was characterized through α_s plots of adsorption isotherms of N₂ gas at 77 K as microporous surface area (S_micro.) due to micropores and external surface area (S_ext.) mainly due to the mesopores. A simple model can be presented by recognizing the different contributions of S_micro. and S_ext. in forming electric-double layers. The capacitance per unit external surface area was larger by one order of magnitude than that per unit surface area of micropores (0.187 F/m² versus 0.017 F/m² at charge-discharge current of 4 mA/g), revealing greater contribution of external surface to specific capacitance for electric-double layers than surface of micropores. With the increase in charge-discharge current to 40 mA/g, the relative contribution of external surface became more significant, which was supposed to be due to large sizes of electrolyte ions, Et₃MeN⁺ and BF₄⁻.     

Direct electrochemistry of guanosine on multi-walled carbon nanotubes modified carbon ionic liquid electrode

A multi-walled carbon nanotubes (MWCNTs) modified carbon ionic liquid electrode (CILE) was fabricated and used to investigate the electrochemical behavior of guanosine. CILE was prepared by mixing hydrophilic ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF₄), graphite powder and liquid paraffin together. The fabricated MWCNTs/CILE showed great electrocatalytic ability to the oxidation of guanosine and an irreversible oxidation peak appeared at 1.067 V (vs. SCE) with improved peak current. The electrochemical behavior of guanosine on the MWCNTs/CILE was carefully studied by cyclic voltammetry and the electrochemical parameters such as the charge transfer coefficient (α) and the electrode reaction standard rate constant (k_s) were calculated with the result as 0.66 and 2.94 × 10⁻⁴ s⁻¹, respectively. By using differential pulse voltammetry (DPV) as the detection method, a linear relationship was obtained between the oxidation peak current and the guanosine concentration in the range from 1.0 × 10⁻⁷ to 4.0 × 10⁻⁵ mol/L with the detection limit as 7.8 × 10⁻⁸ mol/L (3σ). The common coexisting substances showed no interferences to the guanosine detection and the modified electrode showed good ability to distinguish the electrochemical response of guanosine and adenosine.     

High performance nanoporous carbon membranes for air separation

The preparation of porous stainless steel supports was found to have a significant impact on the properties of nanoporous carbon membranes fabricated upon them. Nanofillers were incorporated into porous stainless steel supports to modify the pore structure by reducing the average pore size and porosity. Carbon membrane properties were examined as a function of support variables such as filler content, shape, size and nature of the particles. Optimum performances, in terms of the ideal selectivity ratio for oxygen to nitrogen permeances (S_O2/N2∼3-6) and the oxygen permeance (10⁻⁸ mol m⁻² s⁻¹ Pa⁻¹), were obtained when the filler completely saturated the support. This represents about a two order of magnitude improvement in oxygen permeance when compared to carbon membranes prepared on unmodified porous stainless steel supports. The origin of the improvement in the permeance is due to the formation of carbon membranes which are on average two orders of magnitude thinner than those formed on unmodified supports, i.e., the carbon membranes exists as very thin layers around and between the silica nanoparticles. A simple geometric model based on the packing of silica particles inside the porous stainless steel support is proposed to visualize and quantify this effect. The generality of the support modification concept is also demonstrated by the ability to employ different types of nanofillers and support geometries to obtain carbon membranes with high flux. Air separation experiments show that these membranes can produce both oxygen rich streams enriched to as much as 48% by volume and nitrogen rich streams enriched to over 90% by volume at reasonable operating conditions.     

Methane reforming reaction with carbon dioxide over SBA-15 supported Ni-Mo bimetallic catalysts

A series of mesoporous molecular sieves SBA-15 supported Ni-Mo bimetallic catalysts (xMo1Ni, Ni = 12 wt.%, Mo/Ni atomic ratio = x, x = 0, 0.3, 0.5, 0.7) were prepared using co-impregnation method for carbon dioxide reforming of methane. The catalytic performance of these catalysts was investigated at 800 °C, atmospheric pressure, GHSV of 4000 ml·g_cat^− 1·h^− 1 and a V(CH₄)/(CO₂) ratio of 1 without dilute gas. The result indicated that the Ni-Mo bimetallic catalysts had a little lower initial activity compared with Ni monometallic catalyst, but it kept very stable performance under the reaction conditions. In addition, the Ni-Mo bimetallic catalyst with Mo/Ni atomic ratio of 0.5 showed high activity, superior stability and the lowest carbon deposition rate (0.00073g_c·g_cat^− 1·h^− 1) in 600-h time on stream. The catalysts were characterized by power X-ray diffraction, N₂-physisorption, H₂-TPR, CO₂-TPD, TG and TEM. The results indicate that the Ni-Mo bimetallic catalysts have smaller metal particle, higher metal dispersion, stronger basicity, metal-support interaction and Mo₂C species. It is concluded that Mo species in the Ni-Mo bimetallic catalysts play important roles in reducing effectively the amount of carbon deposition, especially the amount of shell-like carbon deposition.     

Electrochemical enhancement of adsorption capacity of activated carbon fibers and their surface physicochemical characterizations

The adsorption of activated carbon fibers (ACFs) and their surface characteristics were investigated before and after electrochemical polarization. The adsorption kinetics of m-cresol showed the dependence on polarized potential, and the adsorption rate constant increased by 77.1%, from 6.38 × 10⁻³ min⁻¹ at open-circuit (OC) to 1.13 × 10⁻² min⁻¹ at polarization of 600 mV. The adsorption isotherms at different potentials were in good agreement with Langmuir isotherm model, and the maximum adsorption capacity increased from 2.28 mmol g⁻¹ at OC to 3.67 mmol g⁻¹ at polarized potential of 600 mV. These indicated that electrochemical polarization could effectively improve the adsorption rate and capacity of ACFs. The surface characteristics of ACFs before and after electrochemical polarization were evaluated by N₂ adsorption-desorption isotherms, scanning electron microscope (SEM), zeta potential and Fourier transform infrared spectroscopy (FTIR). The results showed that the BET specific surface area and pore size increased as the potential rose. However, the surface chemical properties of ACFs hardly changed under electrochemical polarization of less than 600 mV. This study was beneficial to understand the mechanism of electrochemically enhanced adsorption.     

Activated carbon fiber cloths as electrodes for high performance electric double layer capacitors

Activated carbon fiber cloth (ACFC) electrodes with high double layer capacitance and good rate capability were prepared from polyacrylonitrile (PAN) fabrics by optimizing the carbonization temperature prior to CO₂ activation. The carbonization temperature has a marked effect on both the pore structure and the electrochemical performances of the ACFCs. Moderate carbonization at 600 °C results in higher specific surface area and larger pore size, and hence higher capacitance and better rate capability. The specific capacitance of the ACFCs in 6 mol L⁻¹ KOH aqueous solution can be as high as 208 F g⁻¹. It remains 129 F g⁻¹ as the current density increases to 10 000 mA g⁻¹.     

Detection of NADH via electrocatalytic oxidation at single-walled carbon nanotubes modified with Variamine blue

Screen-printed electrodes (SPEs) modified with Variamine blue (VB), covalently attached to the oxidized single-walled carbon nanotubes (SWCNTs-COOH), were developed and used as chemical sensors for the detection of the reduced nicotinamide adenine dinucleotide (NADH). The Variamine blue redox mediator was covalently linked to the SWCNTs-COOH by the N,N′-dicyclohexylcarbodiimide (DCC) and N-hydroxysuccinimide (NHS) chemistry. Infrared Fourier transform (FT-IR) spectroscopy revealed the presence of the amide bands situated at 1623 cm⁻¹ (I band), 1577 cm⁻¹ (II band) and 1437 cm⁻¹ (III band) demonstrating the covalent linkage of Variamine blue to SWCNTs-COOH. The heterogeneous electron transfer rate, k_obs., was 13,850 M⁻¹ s⁻¹, and the k_s and α were 0.8 s⁻¹ and 0.56, respectively. The pH dependence was also investigated. SPEs modified with Variamine blue by using the DCC/NHS conjugation method, showed a variation of −36 mV per pH unit.A successful application was the development of a lactate biosensor obtained by the immobilization of the l-lactate dehydrogenase on the NADH sensor.     

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.     

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.