Journal of Non-Crystalline Solids 347 (2004) 238245 www.elsevier.

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Capacitance control of carbon aerogel electrodes

Sung-Woo Hwang, Sang-Hoon Hyun
Received 29 July 2003 Available online 22 October 2004

School of Advanced Materials Science and Engineering, Yonsei University, 134 Shinchon-dong, Sudaemoon-ku, Seoul 120-749, Republic of Korea

Abstract Carbon aerogels are promising materials as electrodes for capacitive deionization (CDI) units and electrical double layer capacitors (EDLCs). An optimum process is presented for synthesis of nanoporous carbon aerogels via pyrolyzing resorcinolformaldehyde (RF) organic aerogels, which could be cost-eectively manufactured from RF wet gels by a modied ambient drying technique using acetone exchange/controlled evaporation instead of conventional supercritical drying. The linear shrinkage of RF aerogel during ambient-drying of wet gels was controlled to be less than 4%, almost same as that of supercritical drying. Carbon aerogels obtained by pyrolyzing of RF aerogels (specic surface area 300400 m2/g) retains high specic surface area (400700 m2/g), low density (0.401.16 g/cm3), and ultrane pore size (<50 nm) depending on the pH 3.06.5 range of the starting RF solution. The specic capacitance of carbon aerogel electrodes activated at 450 C in air environment for 1 h has been improved to 220 F/g. 2004 Elsevier B.V. All rights reserved.

1. Introduction Carbon aerogel, i.e. a monolithic three-dimensional mesoporous network of carbon nanoparticles, is considered as a promising material for various electrochemical applications. Carbon aerogels are obtained by the pyrolysis of organic aerogels based on resorcinolformaldehyde (RF), phenolfurfural (PF), phenolresorcinolformaldehyde, melamineformaldehyde (MF), polyurethanes, polyureas, and PVCs via a solgel process [1]. Organic aerogels were prepared rstly by Pekala in 1989 [2]. Their synthesis involved the polymerization of a resorcinolformaldehyde mixture diluted in water with sodium carbonate as a base catalyst. The resorcinol and formaldehyde condense into polymer clusters cross-linked to form a wet gel structure. To obtain RF aerogel, the RF wet gel is dried with supercritical carbon dioxide

Corresponding author. Tel.: +82 2 2123 2850; fax: +82 2 365 5882. E-mail address: prohsh@yonsei.ac.kr (S.-H. Hyun).

to avoid collapse of the pore structure. This supercritical drying process preserves the pore structure of wet gel since the absence of a vaporliquid interface and thus without interfacial tensions. Synthesized RF aerogels are mesoporous materials with high surface area and their structure is composed of interconnected beads with diameters 710 nm [2,3]. However, this supercritical drying with high pressure beyond 1000 psi is complicate, expensive, dangerous and dicult to mass production. Therefore, development and optimization of the ambient drying process for synthesis of RF aerogel is needed. The selection of suitable solvents for exchange with pore water and controlled evaporation of solvent are very important factors for the ambient drying to minimize collapse of the wet gel structure caused by interfacial tension from the presence of liquidvapor interface during drying [4,5]. Carbon aerogels are derived from pyrolysis of RF aerogels in an inert environment. Volumetric/linear shrinkage accompanied by mass loss occurs during pyrolysis. The structure of carbon aerogels consists of a three-dimensional network of interconnected carbon nanoparticles measuring 510 nm in diameter. These

0022-3093/$ - see front matter 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.jnoncrysol.2004.07.075

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carbon aerogels are reported to have very high specic surface area per unit mass (400900 m2/g), low density (0.31.0 g/cm3), good electrical conductivity (550 S/ cm), and high purity (>99.5% carbon) and their possibility of their usage without binding substances [4]. Furthermore, the pore and the particle size of these carbon aerogels could be controlled over a broad range in nanometer scale. A high surface area in combination with a good electrical conductivity of carbon aerogels makes them ideal for applications such as electrode materials in intercalation anodes of rechargeable lithium ion battery [4,6], electrochemical double layer capacitors (EDLCs) [7], fuel cells, and electrosorptive water purication process like capacitive deionization (CDI) [8]. Other potential applications include their usage as absorbents [9] and as materials for chromatographic separation. The objectives of this research include developing a cost-eective process for synthesizing RF aerogels via ambient drying to make optimal carbon aerogels for EDLCs and electrosorptive applications. For this research, the eects of initial pH of the RF solution on the properties of RF aerogels obtained by ambient drying and on the physical/electrochemical properties of the synthesized carbon aerogel electrodes for EDLCs application have been experimentally elucidated.

Resorcinol + Catalyst + D. I Water Formaldehyde Stirring for 1 h

pH adjustment with dilute HNO3 and NH4OH RF solution Wet gel formation at 50C oven for 96 h RF wet gel Solvent exchange with acetone for 96 h Ambient drying at R.T and 50C oven

RF aerogel Pyrolysis at 800C in N2 Environment Carbon aerogel Cutting, polishing and activation Carbon aerogel electrode

2. Experimental The overall experimental procedure for synthesis of organic RF aerogel/carbon aerogel is described as a owchart in Fig. 1. 2.1. Preparation of RF aerogels RF wet gels were prepared with the aqueous polycondensation of resorcinol within formaldehyde using sodium carbonate as a base catalyst. Extra pure reagent grade resorcinol (99%, Yakuri pure chemicals co., ltd.) and formalin (37 wt% formaldehyde solution, stabilized 78% methanol) were mixed in a 1:2 molar ratio, and deionized water was used as a solvent to control the nal concentration. Since sodium carbonate promoted the formation of resorcinol anion by hydrogen abstraction [10], it was mixed with resorcinol and deionized water ahead. After forming a homogeneous solution, formalin was added and the solution was stirred for 1 h. Generally, the catalyst level controls the particle size, and the degree of dilution determines the density of the aerogel [4,11,12]. In this work, the R/C (resorcinol/catalyst) molar ratio was xed by 1000 and solid concentration of the RF solution was xed by 40 wt%. After complete mixing for 1 h, the initial pH of the RF solution was adjusted to the desired level with diluted nitric acid and ammonia water. Synthesized RF solution was decanted

Fig. 1. Overall experimental owchart.

into polyethylene cylindrical vessels. The vessels were sealed with Teon lms, and followed by 96 h of gelation in an oven at 50 C. After gelation, the RF wet gel was removed from the oven and cooled in room temperature. The diameter, thickness, and weight of RF wet gels were measured to evaluate shrinkage behavior during ambient drying process. In preparation for ambient drying, the RF wet gels were placed into a bath of hot acetone (bp = 56.5 C). The acetone was heated to near boiling point to accelerate the diusion of water from the RF wet gel. Multiple exchanges with fresh acetone were used to remove residual water in the pore of RF wet gel for 96 h. Ambient drying was performed at room temperature for 72 h and at 50 C oven for 72 h by controlled evaporation of pore liquid in the acetone environment. Then the diameter, thickness, and weight of the dried RF aerogel were measured to evaluate the density, porosity, and shrinkage during ambient drying. 2.2. Preparation of carbon aerogel electrodes Carbon aerogels were prepared by pyrolysis of RF aerogels. Pyrolysis of the RF aerogels was carried out under continuous nitrogen ow in a tube furnace. The

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RF aerogels were heated to 300 C using a heating rate of 2 C/min, and held there for 2 h, then heated up to 800 C by heating rates of 3 C/min and maintained for another 1 h. The volumetric/linear shrinkages upon pyrolysis were measured. Synthesized carbon aerogels were cut into a disk of 1 mm thickness, using a diamond saw. After cleaning and drying, the carbon aerogel electrodes were activated at 450 C in hot air environment for 1 h to modify surface functionality and improve the anity with the electrolyte. 2.3. Characterization A Micromeritics Gemini III surface area analyzer was used to obtain the specic surface area, pore size distributions, and nitrogen adsorption isotherm at 77 K. Pore size distributions were calculated with the adsorption data based on the BarretJoynerHalenda method [13]. The four-point probe method was used to obtain electrical conductivity of carbon aerogel electrodes at room temperature. The surface morphology and microstructures of synthesized RF/carbon aerogels were observed by Hitachi S4200 scanning electron microscope (SEM). The most common techniques for estimating the capacitance are the following: cyclic voltammetry (I = f(E)), galvanostatic charge/discharge (I = const.), external resistor discharge (R = const.), and impedance spectroscopy [4]. Each technique supplies dierent peculiar performance of capacitor. In this work, a typical galvanostatic charge/discharge method was used to carry out the electrochemical measurement. As electrochemically inert current collectors, 99.9% graphite disks were used. Two carbon aerogel electrodes were separated by a 0.1 mm thick microporous polypropylene membrane, and electrolyte solution. Before any measurements were made, the carbon aerogel electrodes were placed in the 6 M sulfuric acid electrolyte solution for 1 day to ensure complete lling of the porous electrodes. The carbon aerogel electrodes were rmly pressed by stainless steel screws to minimize contact-resistance. This assembly was placed in a Teon cell containing 6 M sulfuric acid solution as the electrolyte. To calculate the specic capacitance, this cell was charged with constant current (10 mA/s) up to a voltage of 1 V, and discharged with constant current (10 mA/s) down to a voltage of 0 V. The specic capacitance of a single carbon aerogel electrode was calculated from this charge/ discharge curve using Eq. (1): I Dt C ; DVm 1

and 1 V with a scan rate of 1 mV/s using a WonATech WBCS 3000 DC battery cycler. The DC battery cycler and the capacitance measurement cell were both connected to a computer, which was used to control parameters and record experimental results. The electrochemical experiments were conducted at room temperature.

3. Results Fig. 2 shows the variation of the gelation time with the initial pH of RF solution. In general, gelation time is function of the solid concentration in the RF solution and the catalyst level [2]. In this experiment, solid concentrations of the RF solution and the R/C ratio were xed 40 wt% and 1000, respectively. As shown in Fig. 2, as the initial pH of RF solution was increased, the gelation time was abruptly decreased. In addition, the initial pH of the RF solution inuences the optical appearances of the RF wet gels/aerogels drastically. Where initial pH of the RF solution less than 6.0, the colors of synthesized RF wet gels were yellowish brown. And initial pH of 6.57.5 range, the colors of RF wet gels were darkish red. The eect of the initial pH of the RF solution on the volumetric/linear shrinkage during ambient drying is given in Fig. 3(a). Samples with initial pH of 3.06.5 shows a linear shrinkage of less than 4%. In contrast, shrinkage of samples with an initial pH over 6.5 was increased signicantly. The shrinkage upon pyrolysis was independent on the initial pH of the RF solution as shown in Fig. 3(b). The volumetric/linear shrinkage during pyrolysis was almost constant of 50% and 22%, respectively. The bulk densities and porosities of the

18 16 14

Gelation Time (h)

12 10 8 6 4 2 0 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 Initial pH of RF solution 7.0 7.5

where C is the specic capacitance (F/g), I is the constant current, Dt is the time period, DV is the potential dierence, and m is the mass of the carbon aerogel electrode. Cyclic voltammetry was performed between 0 V

Fig. 2. Variation of gelation time depending on initial pH of RF solution. The solid concentration of the RF solution was xed 40 wt% and the volume of each solution was xed to 2 cc.

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80 70 Volumetric/Linear Shrinkage (%) 60 50 40 30 20 10 (a) 0 (a) 100 90 Volumetric/Linear Shrinkage (%) 80 70 60 50 40

Volumetric shrinkage Linear shrinkage

Volumetric Shrinkage Linear Shrinkage

1.4 1.2

Bulk Density (g/cm )

1.0 0.8 0.6 0.4 0.2 0.0 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5

Initial pH of RF solution
100 1.4 1.2 90 80 70

4 6 5 Initial pH of RF Solution

Bulk Density (g/cm )

1.0 0.8 0.6 0.4 0.2 0.0 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5

Porosity (%)

60 50 40 30 20 10 0

30 (b) 20 10 0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 Initial pH of Solution 7.5 8.0

Initial pH of RF solution

Fig. 4. Variation of density (j) and porosity (h) of RF/carbon aerogels depending on initial pH of RF solutions: (a) RF aerogels, and (b) carbon aerogels.

(b)

800 Specific Surface Area (m2/g)

Fig. 3. Shrinkage variation with initial pH of RF solution during (a) ambient drying at 50 C in air and (b) pyrolysis at 800 C in N2 atmosphere.

700 600 500 400 300 200 100 0 2.5 3.0 3.5

BET Multipoint Surface Area Micropore Area

RF/carbon aerogels were depend on the shrinkage behavior during ambient drying, obviously. As given in Fig. 4(a) and (b), the tendency of bulk density/porosity versus initial pH of the RF solution was almost the same with that of shrinkage. In the case of the initial pH under 6.5, bulk densities and porosities of carbon aerogels were 0.430.48 g/cm3 and 7880%, respectively. The dependence of the specic surface area of carbon aerogels on the initial pH of the RF solution is depicted in Fig. 5. The specic surface area was slightly increased in the range of the initial pH 3.05.5. However, above pH 5.5, the specic surface area of carbon aerogels was decreased drastically. At initial pH of 5.5, the specic surface area was highest (610 m2/g) and the micropore area fraction was lowest. Other physical properties of synthesized RF/carbon aerogels with various initial pH are given in Table 1.

4.0 4.5 5.0 5.5 6.0 Initial pH of RF solution

6.5

7.0

7.5

Fig. 5. Variation of the specic surface area of carbon aerogels with the initial pH of RF solutions.

The nitrogen adsorption isotherm and the pore size distribution of two carbon aerogels synthesized with an initial pH of 5.5 and 6.5 are shown in Fig. 6.

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Table 1 Physical properties of the synthesized RF/carbon aerogels Initial pH of RF solution 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5
a b c

Linear shrinkage during ambient drying (DL/L,%) 3.10 3.71 3.57 3.03 3.06 4.76 4.08 4.08 22.89 25.95

Density of RF aerogel (g/cm3) 0.49 0.48 0.48 0.43 0.46 0.44 0.44 0.44 0.85 0.86

Density of carbon aerogel (g/cm3) 0.44 0.51 0.49 0.46 0.49 0.50 0.46 0.46 1.07 1.16

SBETa (m2/g)

SMicrob (m2/g)

Electrical conductivityc (S/cm) 15.84 8.98 13.81 15.67 12.75 13.18 8.56 5.80 9.08

478.75 502.31 518.60 506.38 517.90 610.14 592.00 538.97 34.22

385.67 385.64 366.40 349.83 349.23 355.72 378.30 318.91 2.47

BET multipoint specic surface area. Micropore area. Measured by 4-point probe technique (all values were corrected for disk-type sample).

300 250 200 150 100 50 0 0.0 0.2 0.4 0.6 Relative Pressure (P/Po) 0.8

(a)

Differential Pore Volume (cm3g-1nm-1)

0.06 0.05 0.04 0.03 0.02 0.01 0.00

Initial pH 5.5 Initial pH 6.5

(b)

8 10 12 Pore Diameter (nm)

14

16

18

For the carbon aerogel with an initial pH of 5.5, it showed a larger dierential pore volume at 2 nm in pore diameter compared to that of the carbon aerogel with an initial pH of 6.5. Fig. 7 shows a morphologies and microstructures of the RF/carbon aerogels obtained at dierent initial pH. The highly porous network structure with continuous porosity and coagulated particle size less than 100 nm was maintained after pyrolysis, as shown in Fig. 7(a)(c). In contrast, for the carbon aerogel derived from initial pH of 7.0, it had a highly dense structure and almost no pores were observed from the SEM micrographs, as given in Fig. 7(d). The specic capacitance according to initial pH of the RF solution is shown in Fig. 8. For carbon aerogel in pH 5.5, high value of capacitance (220.4 F/g) was obtained in the 6 M sulfuric acid electrolyte. Fig. 9 shows a cyclic voltammogram for the carbon aerogel electrodes with activated at 450 C and no heat-treated carbon aerogel electrodes in the 6 M sulfuric acid electrolyte. A regular, almost box-like shape of the curve has been observed which carbon aerogel electrodes with no post heat-treatment in air atmosphere after pyrolysis procedure. In case of air-activated carbon aerogel electrodes, the voltammetry characteristics of the capacitor are slightly changed. Instead of typical rectangular shape, a slight remarkable region of reversible surface faradaic reaction was observed at around 0.2 V.

Fig. 6. The N2 adsorption isotherm (initial pH = 5.5) and pore size distributions of carbon aerogels synthesized with an initial pH of 5.5 and 6.5.

Volume Adsorbed (cc/g at STP)

4. Discussion The eect of pH on the solgel chemistry involving a reaction in between resorcinol and formaldehyde, and the mechanism of the reaction has been already studied [2,14]. In general, gelation time is a function of the solid concentration in the solution and the catalyst level [2]. In this work, since solid concentration was xed by

Cryogenic nitrogen isotherm of carbon aerogel with the initial pH of 5.5 appears to exhibit a type IV nitrogen adsorption isotherm. The pore size distribution given in Fig. 6(b) shows a majority of pore volume was associated with pores ranging from pore diameter of 25 nm.

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Fig. 7. SEM micrographs of the RF/carbon aerogels: (a) RF aerogel (initial pH = 6.0), (b) carbon aerogel (initial pH = 6.0), (c) carbon aerogel (initial pH = 5.5), and (d) carbon aerogel (initial pH = 7.0).

250 220.4 F/g

0.05 Activated carbon aerogel electrode 0.04

200 Specific Capacitance (F/g)

Current (A)

0.03 0.02 0.01 0.00 -0.01 -0.02 No heat -treated

150

100

50

o After Activation at 450 C in Air for 1h

-0.03 0.0 0.2 0.4

Scan Scan rate rate = =1 1 mV/sec mV/sec 0.6 0.8 1.0

0 2.5

Potential (V)

3.0

3.5

4.0 4.5 5.0 5.5 6.0 Initial pH of RF Solution

6.5

7.0
Fig. 9. Cyclic voltammogram in 6 M sulfuric acid electrolyte of synthesized carbon aerogels derived from initial pH of 5.5: (a) heat treated at 450 C in air environment for 1 h and (b) no heat treated (scan rate = 1 mV/s).

Fig. 8. Plot of the specic capacitance versus initial pH of RF solution for carbon aerogel electrodes synthesized at various initial pH.

40 wt% and the R/C ratio was xed by 1000, only initial pH of the RF solution eects on the gelation time. Since high solid concentration (40 wt%) of the prepared RF solution, the polymerization of resorcinolformaldehyde occurs in wide pH range (pH 3.07.5). The linear shrinkage during ambient drying is less than 4% in the range of pH 3.06.5, as shown in Fig. 3. In the case of supercritical drying using liquid carbon dioxide, linear shrinkage is reported to less than 3% [15]. Compared to above result, ambient drying technique used in this experiment, which contains multiple solvent

exchanges with hot acetone, and controlled evaporation in acetone atmospheres was good enough to the supercritical drying of CO2. Solvent exchanges with ultrasound or continuous mechanical agitation would be expected to reduce the time required for ambient drying process. Linear shrinkage during ambient drying, bulk density of RF aerogel, and bulk density/porosity of carbon aerogel derived from the RF wet gels prepared with an initial pH higher than 7.0 is not able to withstand the mechanical stress during ambient drying and pyrolysis procedure which clearly caused the nanostructures to

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collapse, and lead to carbon aerogels having almost no surface area [14]. On the other hand, the initial pH below 6.5, highly cross-linked and very tough pore structure was formed, where the majority of the pore remained intact even after the ambient drying and pyrolysis process. Figs. 35 and Table 1 are compatible with these results. The pore size distribution of the material strongly inuences to the nitrogen adsorption data and the electrochemical behavior. It is proved [16] that the carbon aerogels with pore diameter between 3 and 13 nm have the best voltammetry characteristics and the highest capacitance values. Type IV nitrogen adsorption isotherm of carbon aerogel electrode derived from initial pH of 5.5 which is described in Fig. 6(a) is usually ascribed to capillary condensation occurring in mesopores and resembles in those inspected for solgel derived inorganic oxide aerogels. But, as described in Table 1, micropore area fraction is very high (6080%) for synthesized carbon aerogels. It has been studied that pores larger than 2 nm in diameter may be suitable in aqueous electrolyte, and in organic electrolytes, which have been limited to pores larger than 5 nm in diameter [17]. In principle, the pores larger than 0.5 nm could be accessible electrochemically for aqueous electrolyte. However, because of overlapping eect, an electrical double layer could not be fully developed in the micropores [18,19]. Therefore, the existence of micropore reduces signicantly overall electrochemical capacitance of the EDLCs. In this experiment, both of the carbon aerogels derived from initial pH of 5.5 and 6.5 have suitable pore structures for electrochemical capacitor using aqueous electrolytes. However, the micropore area is lowest and total specic surface area is highest at the carbon aerogel with initial pH of 5.5, it would be expected more larger specic capacitance than that of carbon aerogel with initial pH of 6.5. The mesoporous network structure of RF aerogels is not aected drastically during pyrolysis. Still high porous nanostructures of carbon aerogels are observed even after pyrolysis, in which the carbon particle size is around 20 nm in diameter from the SEM micrographs as given in Fig. 7. But in the case of initial pH of 7.0, almost no pores are observed and it looks like a sintered structure. The low specic surface area and high density of this gel indicates the nonporous structure. These results are consistent with the low condensation reaction rate with high pH promote a loose cross-linked network structure which is collapsed during ambient drying and pyrolysis [14]. Figs. 8 and 9 reveals the eect of specic surface area and pore size distribution of carbon aroused from synthetic pH and hot air activation on electrochemical properties. The values of specic capacitance could be enhanced through an additional treatment. The functionalization of the carbon surface by a heat treatment at

450 C in air atmosphere causes an improvement of the specic capacitance through the psuedocapacitance eect. The following reactions of electroactive surface functional group could be considered as [20]: C OH ( ) > C @ O H e COOH ( ) COO H e > C @O e ( ) > C O In the case of carbon aerogel electrodes derived from initial pH of 5.5 which is activated at 450 C in air environment for 1 h, it has very high specic capacitance (220.4 F/g) in spite of only pure carbon aerogel, caused by its highest specic surface area, lowest micropore area fraction, and suitable for size for EDLCs. An ideal double layer capacitance behavior of an electrode material is expressed in the form of a rectangular shape on the voltammetry characteristics. The sign of current is immediately reversed upon reversal of the potential sweep. In this type of energy storage, the phenomenon is purely electrostatic and current is independent on the potential [21]. In the case of normal carbon aerogel electrodes, most of ideal rectangular shape on voltammetry characteristics of carbon aerogel electrodes activated at 450 C in air atmosphere for 1 h were detected a small deviation pointed out from such a rectangular shape and reversible redox peaks consisted with surface faradaic reactions. However, more details and exact researches are needed to clarify these phenomena.

5. Conclusions The main ndings from this research on the capacitance control of carbon aerogels electrodes were as follows: (1) Defect free resorcinolformaldehyde (RF) aerogels (density of 0.450.85 g/cm3 and porosity of 60 70%) have been synthesized via modied ambient drying of RF wet gels (RF solid concentration of 40 wt%, resorcinol/catalyst molar ratio of 1000, starting solution of pH 3.07.5 range) instead of conventional supercritical drying. The linear shrinkage occurred during ambient drying process of RF wet gels to make RF aerogels could be controlled below 4%, almost equivalent to the supercritical drying using liquid carbon dioxide. (2) The specic surface area and pore structure of carbon aerogels varies sensitively with the pH of the starting RF solution, while their densities ($0.5 g/ cm3) and porosities ($80%) were found to be almost constant in the range of pH 3.06.5. (3) The specic capacitance of synthesized carbon aerogel electrodes was dependent upon starting pH of the RF solution, in the range of pH 3.06.5. and the

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highest capacitance (220.4 F/g) was obtained at carbon aerogel electrodes derived from pH 5.5 solutions, which are activated at 450 C in air for 1 h. (4) These carbon aerogel electrodes have a little of additional psuedocapacitance eect connected with the faradaic reactions of surface functional groups, in company with their original electrical double layer capacitance.

Acknowledgment This work was supported by Korea Research Foundation Grant (KRF-2002-041-D00274).

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