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.     

EDLC performance of carbide-derived carbons in aprotic and acidic electrolytes

This study shows that carbide-derived carbons (CDCs) with average pore size distributions around 0.9-1 nm and effective surface areas of 1300-1400 m² g⁻¹ provide electrochemical double-layer capacitors with high performances in both aqueous (2M H₂SO₄) and aprotic (1M (C₂H₅)₄NBF₄ in acetonitrile) electrolytes.In the acidic electrolytic solution, the gravimetric capacitance at low current density (1 mA cm⁻²) can exceed 200 F g⁻¹, whereas the volumetric capacitance reaches 90 F cm⁻³. In the aprotic electrolyte they reach 150 F g⁻¹ and 60 F cm⁻³.A detailed comparison of the capacitive behaviour of CDCs at high current density (up to 100 mA cm⁻²) with other microporous and mesoporous carbons indicates better rate capabilities for the present materials in both electrolytes. This is due to the high surface area, the accessible porosity and the relatively low oxygen content.It also appears that the surface-related capacitances of the present CDCs in the aprotic electrolyte are in line with other carbons and show no anomalous behaviour.     

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.     

Bimodal, templated mesoporous carbons for capacitor applications

Several high capacitance ordered mesoporous carbon (OMC) materials, containing a bimodal pore distribution, were synthesized directly using hexagonal mesoporous silicas (HMS) as the template material. The HMS templates were formed using amine surfactants (C_nH_2n+1NH₂) with hydrophobic chain lengths containing 8-16 carbons (n = 8-16). These HMS structures were found to have an interconnected wormhole structure, high textural mesoporosity, a surface area ranging from 910 to 1370 m²/g, and a total pore volume of 1.09-1.83 cm³/g. Also, evidence for a change in structure from hexagonally ordered to layered (for surfactants of chain length with n > 12) was found. The resulting OMCs, formed using sucrose as the carbon precursor, contain bimodal pores 1.6-1.8 and 3.3-3.9 nm in diameter and have a very high surface area (980-1650 m²/g). The OMCs were evaluated as electrode materials for electrochemical capacitors using cyclic voltammetry in 0.5 M H₂SO₄ solution, giving a tunable gravimetric capacitance that increased linearly with BET area (and surfactant chain length), up to 260 F/g, among the highest yet reported for ordered carbon formed from an HMS templated precursor. All OMCs studied in this work displayed a specific capacitance of ∼0.15 F/m².     

Resorcinol-formaldehyde based porous carbon as an electrode material for supercapacitors

Porous carbon materials were prepared using resorcinol and formaldehyde catalyzed by KOH in a sol-gel process followed by carbonization, during which the KOH serves as an activating agent and generates pores mainly located in the micropore range. With an increase of mass ratio of KOH to resorcinol from 1 to 4, both the specific surface area and the pore volume of the carbons increased, from 522 to 2760 m²/g and 0.304 to 1.347 cm³/g, respectively, but the average pore diameter decreased from 4.4 to 2.5 nm. Samples were investigated as electrode materials in supercapacitors and the relevant electrochemical behavior was characterized by cyclic voltammetry, electrochemical impedance spectroscopy and constant current charge-discharge experiments using 30% KOH aqueous solution as electrolyte. The highest specific capacitance of up to 294 F/g was obtained at a current density 1 mA/cm² for the sample with mass ratio of KOH to resorcinol of 2. Only a slight decrease in capacitance for the same sample, from 294 to 242 F/g, was observed when the current density increased from 1 to 30 mA/cm². The specific capacitance only decayed 3% at a current density 30 mA/cm² after 1000 cycles, which indicates that the sample possesses excellent power property and cycle durability.     

Mesoporous RuO2 for the next generation supercapacitors with an ultrahigh power density

The 3D mesoporous, well crystalline RuO₂ film prepared via the evaporation-induced self-assembled method (EISA) successfully demonstrates the extremely high power performances (e.g., excellent capacitive behavior at 10,000 mV s⁻¹, ultrahigh-frequency capacitive responses (the absence of a knee point in the Nyquist plot), and 2.6 MW kg⁻¹ with an acceptable energy density of 4.6 Wh kg⁻¹). These excellent capacitive performances were identified by means of voltammetric and electrochemical impedance spectroscopic (EIS) analyses. The mesoporous (with mean pore spacing of 18.1 nm) and crystalline nature of this film was characterized by means of the field emission scanning electron microscopy (FE-SEM), Brunaur-Emmett-Teller (BET) method, small-angle X-ray scattering (SAXRS), high-resolution transmission electron microscopy (HR-TEM), electron diffraction (ED), and X-ray diffraction (XRD) analyses. This mesoporous, well crystalline RuO₂ film constrains the redox transition to the superficial region meanwhile the tailored mesoporous structure increases the electrochemically active centers, promotes the penetration of electrolytes, provides the “proton reservoirs”, and enhances the rate of electron transport simultaneously for the ultrahigh power application. The specific capacitance of this mesoporous RuO₂ can be enhanced from 84 to 185 F g⁻¹ after the microwave-assisted hydrothermal treatment.     

Optimisation of supercapacitors using carbons with controlled nanotexture and nitrogen content

In order to optimize the performance of supercapacitors, the capacitance of the carbon materials used as electrodes was strictly related to their pores size and also to their redox properties. Well-sized carbons have been elaborated through a template technique using mesoporous silica. For a series of template carbons, a perfect linear dependence has been found for the capacitance values versus the micropore volume determined by CO₂ adsorption. The redox properties of carbons were enhanced by substituting nitrogen for carbon up to ca. 7 wt.%. For carbons with similar nanotextural characteristics, the electrochemical measurements showed a proportional increase of the specific capacitance with the nitrogen content in acidic electrolyte. For an activated carbon from polyacrylonitrile with a specific surface area of only 800 m² g⁻¹, but with a nitrogen content of 7 wt.%, the capacitance reaches 160 F g⁻¹, with very little fading during cycling.     

Effect of mesoporosity on specific capacitance of carbons

The study compares the structural and electrochemical properties of 12 porous carbons based on phenolic resins, using both aqueous (H₂SO₄) and aprotic ((C₂H₅)₄NBF₄ in acetonitrile) electrolytes. It appears that they fit into the general pattern observed for other carbons. The present carbons have micropore volumes varying between 0.29 and 0.66 cm³ g⁻¹ and average pore widths L_o between 0.62 and 1.23 nm. Five samples are exclusively microporous, whereas seven also display a relatively important mesoporosity. This allows a direct comparison between pairs of carbons with similar micropore systems, with and without mesopores, in order to assess the role of mesoporosity in the electrochemical properties. It appears that mesopores have only a limited influence on the decrease in capacitance at high current density as opposed to earlier assumptions.     

High power supercapacitors using polyacrylonitrile-based carbon nanofiber paper

Porous carbon nanofiber paper has been obtained by one-step carbonization/activation of PAN-based nanofiber paper at temperatures from 700 to 1000 °C in CO₂ atmosphere. The paper was used as supercapacitor electrode without any binder or percolator. At low temperature, e.g., ?900 °C, nitrogen enriched carbons with a poorly developed specific surface area (S_BET ? 400 m²/g) are obtained. In aqueous electrolytes, these carbons withstand high current loads without a noticeable decrease of capacitance, and the normalized capacitance reaches 67 μF/cm². At 10 s time constant, the values of energy and power densities are 3-4 times higher than for activated carbons (AC) presenting higher specific surface area. By carbonization/activation at 1000 °C, subnanometer pores are developed and S_BET = 705 m²/g. Despite moderate BET specific surface area, the capacitance reaches values higher than 100 F/g in organic electrolyte. At high power densities, the nanofiber paper obtained at 1000 °C outperforms the energy density retention of ACs in organic electrolyte. The high power capability of the carbon nanofiber papers in the two kinds of electrolytes is attributed both to the high intrinsic conductivity of the fibers and to the high diffusion rate of ions in the opened mesopores.     

A novel high power symmetric ZnO/carbon aerogel composite electrode for electrochemical supercapacitor

We present, for the first time, a new material of symmetric electrochemical supercapacitor in which zinc oxide (ZnO) with carbon aerogel (CA) was used as active material. Physical properties of ZnO/CA composite were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). It was found that ZnO has single hexagonal structure and the grain size increases with increase of ZnO compository. The result of cyclic voltammetry indicates that the specific capacitance of ZnO/CA composite in 6 M KOH electrolyte was approximately 25 F/g at 10 mV/s for 2:1 composition. AC impedance analysis reveals that ZnO with carbon aerogel powder enhanced the conductivity by reducing the internal resistance. Galvanostatic charge/discharge measurements were done at various current densities, namely 25, 50, 75, and 100 mA/cm². It was found that the cells have excellent electrochemical reversibility and capacitive characteristics in KOH electrolyte. The maximum capacitance of the ZnO/CA supercapacitor was 500 F/g at 100 mA/cm². It has been observed that the specific capacitance is constant up to 500 cycles at all current densities, which implies that the dendrite formation was controlled.     

Electrochemical properties of an ordered mesoporous carbon prepared by direct tri-constituent co-assembly

An ordered mesoporous carbon with a high surface area of 2390 m²/g and a large pore size of 6.7 nm was synthesized through an organic-inorganic-surfactant tri-constituent co-assembly method which used resols as the carbon precursor, silicate oligomers as the inorganic precursor and triblock copolymer as the soft template. The electrochemical properties of this carbon were evaluated as an electrode material for electrochemical double layer capacitor and lithium-ion battery. It shows rectangular-shaped cyclic voltammetry curves over a wide range of scan rates even up to 200 mV/s between 0 and 3 V, with a large capacitance of 112 F/g in nonaqueous electrolyte. As a negative electrode material for lithium-ion battery, it delivers a reversible specific capacity as high as 1048 mAh/g and a good cycling ability with capacity retention of 500 mAh/g over 50 cycles.     

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.     

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.     

Activation of coal tar derived needle coke with K2CO3 into an active carbon of low surface area and its performance as unique electrode of electric double-layer capacitor

Raw needle coke from coal tar pitch was activated with K₂CO₃ at a coke:carbonate weight ratio of 1:4, to prepare an electrode for an electric double-layer capacitor (EDLC). Although the surface area of the coke activated at 900 °C for 3 h was as small as 20 m²/g, with a very high yield, the coke achieved capacitances per weight and volume of 20 F/g and 20 F/ml, respectively, in the two-electrode system, by charging at 2.7 V. The surface area of KOH-activated coke with a similar ratio (coke:hydroxide = 1:4, wt:wt) was over 2300 m²/g, and it exhibited capacitance per weight and volume values of 42 F/g and 17 F/ml, respectively. The coke activated by K₂CO₃ was found to be further activated by the charging. This electrochemical activation, which has been reported as activation in an electric field, was investigated by cyclic voltammetry in order to clarify it. The graphitic and pore structures of the coke after the electrochemical activation were analyzed by XRD to confirm retention of the graphene structure. Xe-NMR showed that the formation of small new pores was induced in the cathode material, increasing the surface area from 6 m²/g to 18 m²/g before use, although the pore volume was around 0.015-0.017 m³/g both before and after the charging. This activation with K₂CO₃ and a deeper understanding of the activation on charging suggest future directions for the preparation of electrode carbon for EDLCs.     

Characterization of pistachio shell-derived carbons activated by a combination of KOH and CO2 for electric double-layer capacitors

The micropores and surface oxygen functional groups of KOH-activated carbons were respectively extended and desorbed by the gasification of CO₂ during the activation process of chars derived from pistachio shells. These activated carbons (ACs) were found to exhibit ideal capacitive performances (i.e., a rectangular shape of CVs at a wide range of scan rates, high power property, and excellent reversibility) in aqueous electrolytes for electric double-layer capacitors. Although the specific capacitance of these ACs measured at a low scan rate (25 mV s⁻¹) is decreased with reducing the density of surface functional groups, the ideal capacitive characteristics can be maintained at a much higher scan rate (300 mV s⁻¹) when the CO₂ gasification time is equal to or longer than 30 min because of the relatively high proportion of mesopores.     

Investigation of thin sputtered Mn films for electrochemical capacitors

Pseudocapacitive manganese oxide films have been synthesized by anodic oxidation of metallic films deposited by sputtering. Results are presented from an electrochemical investigation into properties of these thin sputtered manganese films. Mn films with thickness ranging from 20 to 200 nm have been sputtered onto Pt coated Si wafers in an Argon atmosphere. Electrochemical oxidation converts the metal film into a porous, dendritic structure which displays significant pseudocapacitance. We have observed a specific capacitance (C_s) of 700 F/g when cycled very slowly at a constant current density of 160 μA/cm². The same films probed by cyclic voltammetry (CV) at a rate of 5 mV/s yielded a lower specific capacitance of 400-450 F/g. Post-oxidation material loading was measured to be in the range of 25-75 μg/cm².     

Electrochemical performances of poly(3,4-ethylenedioxythiophene)-NiFe2O4 nanocomposite as electrode for supercapacitor

Poly 3,4-ethylenedioxythiophene (PEDOT)-based NiFe₂O₄ conducting nanocomposites were synthesized and their electrochemical properties were studied in order to find out their suitability as electrode materials for supercapacitor. Nanocrystalline nickel ferrites (5-20 nm) have been synthesized by sol-gel method. Reverse microemulsion polymerization in n-hexane medium for PEDOT nanotube and aqueous miceller dispersion polymerization for bulk PEDOT formation using different surfactants have been adopted. Structural morphology and characterization were studied using XRD, SEM, TEM and IR spectroscopy. Electrochemical performances of these electrode materials were carried out using cyclic voltammetry at different scan rates (2-20 mV/s) and galvanostatic charge-discharge at different constant current densities (0.5-10 mA/cm²) in acetonitrile solvent containing 1 M LiClO₄ electrolyte. Nanocomposite electrode material shows high specific capacitance (251 F/g) in comparison to its constituents viz NiFe₂O₄ (127 F/g) and PEDOT (156 F/g) where morphology of the pore structure plays a significant role over the total surface area. Contribution of pseudocapacitance (C_FS) arising from the redox reactions over the electrical double layer capacitance (C_DL) in the composite materials have also been investigated through the measurement of AC impedance in the frequency range 10 kHz-10 mHz with a potential amplitude of 5 mV. The small attenuation (∼16%) in capacitance of PEDOT-NiFe₂O₄ composite over 500 continuous charging/discharging cycles suggests its excellent electrochemical stability.     

Synthesis of mesoporous carbon spheres with a hierarchical pore structure for the electrochemical double-layer capacitor

Mesoporous carbon spheres with hierarchical foam-like pore structures have been synthesized by a dual-templating strategy using phenolic resol as a carbon source, Pluronic F127 and spherical silica mesocellular foams (Si-MCFs) as the soft and hard template, respectively. The results show that the morphology and mesostructure of the silica template are faithfully replicated. The obtained mesoporous carbon material with spherical diameter size of ca. 3–5 μm exhibits hierarchical pore sizes (from ca. 3.5 to 60 nm), high specific surface area (1320 m²/g) and large pore volume (3.5 cm³/g). The carbon surface contains plenty of oxygen-containing groups, resulting in hydrophilic property for an electrode material. In addition, Pluronic F127 plays an important role in the synthesis for maintaining the foam-like mesostructure of the silica templates and faithful replication of the spherical morphology. The electrochemical measurements show that the hierarchically mesoporous carbon spheres as an electrochemical double-layer capacitor (EDLC) electrode present a long cyclic life, excellent rate capability, and high specific capacitance as ca. 208 F/g at 0.5 A/g in (2.0 M) H₂SO₄ aqueous solution. Its specific capacitance can still remain ca. 146 F/g at a high loading current density of 30 A/g with the retention of ca. 70%. Furthermore, this material also exhibits excellent capacitive performance in (C₂H₅)₄NBF₄/propylene carbonate electrolyte, and its specific capacitance is 97 F/g at loading current density of 0.5 A/g.     

Capacitive performance of mesoporous carbons derived from the citrates in ionic liquid

Mesoporous carbons with different pore structures are prepared via a simple pyrolysis process using citrate salts as precursors. BaC-T carbons derived from barium citrate possess large pore volume and typical multimodal pore size distribution (PSD), while MgC-T carbons derived from magnesium citrate possess high specific surface areas due to their dominant small mesopores and micropores. The capacitive performance of the prepared carbons is investigated in ionic liquid and high specific capacitances (maximum of 180.3 F g⁻¹ for MgC-700) are achieved. Experimental data demonstrate that porosity and surface chemistry corporately determine the capacitive performance. BaC-700 and BaC-800 present good rate performance, and exhibit energy densities of about 50 Wh kg⁻¹. The good capacitive performance of these carbons is attributed to their bimodal PSD with large pore size and appropriate surface properties. The MgC-800 and BaC-800 carbons present good durability of capacitance during three thousand of charge/discharge cycles.     

Varying carbon structures templated from KIT-6 for optimum electrochemical capacitance

Bicontinuous ordered mesoporous carbons (OMCs), fabricated from a KIT-6 template using aluminosilicate as catalyst and furfuryl alcohol as carbon source, were successfully prepared and studied as electrodes in supercapacitors. Their structures were characterized by transmission electron microscopy (TEM), small-angle X-ray diffraction (SAXD) and N₂ cryosorption methods. Using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), the capacitive performance of the OMCs was found to be strongly dependent on the mesostructure. Specific capacitance value greater than 130 F g⁻¹ at 20 mV s⁻¹ were obtained from an OMC that featured high surface area with the existence of additional large pores to enhance the specific capacitance at high discharge rate. For the OMC with the best performance, we found that a power density as high as 4.5 kW kg⁻¹ at an energy density of 6.1 Wh kg⁻¹ can be delivered when the discharge current density is 20 A g⁻¹ and can also be continuously charged and discharged with little variation in capacitance after 2500 cycles. These results indicate that this OMC with optimized structure has potential to be used as a power component in electric vehicles.