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The Fabrication and Characterization of Carbon Aerogels by Gelation and Supercritical Drying in Isopropanol**
By Ruowen Fu, Bo Zheng, Jie Liu, Mildred S. Dresselhaus,* Gene Dresselhaus, Joe H. Satcher, Jr., and Theodore F. Baumann
We report a new method for the fabrication of carbon aerogels. Resorcinol and furfural were polymerized in isopropanol using HCl as a catalyst and the resulting alcogels were then dried directly using supercritical isopropanol, followed by carbonization under a nitrogen atmosphere. The carbon aerogels can be prepared over a range of densities (0.1480.746 g/cm3), depending on the gelation temperature and the mass content of the reactants. The textural and transport properties of the aerogels materials were characterized by nitrogen adsorption/desorption analysis, high-resolution transmission electron microscopy (HRTEM), magnetic susceptibility, and resistivity measurements. TEM observations show that the carbon aerogels are composed of interconnected nanoparticles with diameters ranging from 20 to 30 nm. All of the aerogel samples exhibit high Brunauer EmmettTeller (BET) surface areas in the range of 557656 m2/g. The carbon aerogels produced by this new method have similar transport properties to those of carbon aerogels prepared by the traditional method.

1. Introduction
Carbon aerogels (CA) are novel mesoporous materials with many interesting properties, such as low mass densities, continuous porosities, high surface areas, and high electrical conductivity.[14] These properties are derived from the aerogel microstructure, which is a network of interconnected primary particles with characteristic diameters between 3 and 25 nm. Because of their unusual chemical and textural characteristics, carbon aerogels are promising materials for use as electrode materials for supercapacitors and rechargeable batteries, advanced catalyst supports, adsorbents, chromatographic packing, thermal insulators, and a variety of other applications.[512] Carbon aerogels are typically prepared through the solgel polymerization of resorcinol with formaldehyde in aqueous solution, followed by supercritical drying with liquid CO2, and carbonization at elevated temperatures under a N2 atmosphere.[1] This multi-step procedure can be a time-consuming

[*] Prof. M. S. Dresselhaus, Prof. R. Fu, Dr. G. Dresselhaus Massachusetts Institute of Technology 77 Massachusetts Ave., Cambridge, MA 02139 (USA) E-mail: millie@mgm.mit.edu Prof. R. Fu PCFM Laboratory, Zhongshan University Guangzhou, 510275 (P.R. China) B. Zheng, Prof. J. Liu Department of Chemistry, Duke University Durham, NC 27708 (USA) Dr. J. H. Satcher, Jr., Dr. T. F. Baumann Lawrence Livermore National Laboratory PO Box 808, Livermore, CA 94551 (USA)

[**] The research at MIT was supported by the Lawrence Livermore National Laboratory (LLNL) subcontract B518047 and was partially supported by the National Natural Science Foundation of China (59973028) and by the Talents Training Program Foundation of the Higher Education Department of Guangdong Province, China. Work at Duke University was in part supported by a grant from NASA (NAG-1-01061) through a subcontract from UNC.

process because a solvent exchange is usually required prior to the super-critical drying step. Since water and liquid CO2 are immiscible, the water in the pores of the gel has to be exchanged with an organic solvent such as acetone. Based on this fact, recent efforts have focused on developing more straightforward methods for the preparation of organic aerogels. For example, Droege[13] reported the preparation of low-density gels dried directly at ambient pressure. Pekala et al.[14] reported a solvent-exchange method for the preparation of intermediate to high-porosity xerogels that were dried below supercritical pressures, but having the properties of aerogels typically dried using supercritical conditions. In the work presented here, our goal was to develop a new method that would allow for the fabrication of carbon aerogels in a faster and easier process than traditional techniques. To that end, we synthesized organic gels from resorcinol and furfural in isopropanol and then dried them directly in supercritical isopropanol. The organic aerogels obtained from this process could then be carbonized under an inert atmosphere to produce the carbon aerogels. This approach presents several advantages compared to traditional methods for the preparation of organic and carbon aerogels. First, this technique bypasses the solvent exchange step required for the carbon dioxide supercritical drying process. In addition, since there is no mixing of solvents, pure isopropanol can be recovered during the drying step and reused, thus reducing the cost of the process and minimizing the waste generated by the technique. Another motivation for this work is that this method can be applied to the preparation of aerogel composites. For example, we are interested in using carbon nanotubes (CNTs) to structurally reinforce the architecture of low-density carbon aerogels. Since fluorine-modified carbon nanotubes are soluble in isopropanol, this process should facilitate the incorporation of CNTs into the aerogel matrix. This approach can also be used to introduce other materials, such as activated carbon fibers into the carbon aerogel structure. In this report, we present the details of this

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R. Fu/Carbon Aerogels via Gelation and Drying in Isopropanol new process as well as the textural and transport properties of organic and carbon aerogels prepared by this new method.
20 gelation time (min) 15 10 5 0 40 50 60 70 gelation temperature (C) 1 10 100 gelation time (min)

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2. Results and Discussion

2.1. Effects of Reaction Conditions on Mass Density Typically, organic aerogels are synthesized in aqueous solution through the solgel polymerization of resorcinol with formaldehyde using a base catalyst.[1] In our initial reactions, we investigated potassium hydroxide as a catalyst for the polymerization of resorcinol and furfural in isopropanol. Unfortunately, we were unable to induce gelation with a base under a variety of conditions. Because of this, we chose to use HCl as the catalyst for the synthesis of gels in isopropanol, similar to previous work on novolak resinfurfural systems.[15,16] When the reactants were mixed at 20 C for 30 min and then aged at 70 ~ 75 C for 90 h, dark-red organic alcogels were obtained. After drying these gels directly under supercritical isopropanol, we found that the mass densities of the aerogels were higher than we had anticipated based on the starting formulation (730893 mg mL1) (see Table 1). To determine if the new processing technique was responsible for the increased mass density, we processed alcogels prepared under identical conditions using the traditional carbon dioxide supercritical drying method. The mass densities of these aerogels were also higher than expected. These observations indicate that the gels polymerized at room temperature consist mainly of linear polymeric chains with minimal crosslinking between chains and, as a result, the gels shrink during the drying process. Therefore, to minimize the shrinkage of the gels during drying, the crosslinking density within the gel architecture must be increased. We determined that increasing the reaction temperature resulted in a decrease in the shrinkage of the gels during processing. Presumably, the higher polymerization temperatures promote inter-chain reactions, thereby improving the structural integrity of the gels over the materials prepared at room tem-

Fig. 1. The effect of the gelation temperature on the gelation time.

12

gelation time (min)

8 4 0

60 C 70 C

10 20 mass content (wt%)

30

Fig. 2. Effect of the mass content of reactants on the gelation time.

gelation time (min)

4 2 0

0.5 1 1.5 HCl amount (vol.-%)

Fig. 3. Effect of the amount of HCl used on the gelation time.

perature. Not surprisingly, we also found that the gelation time (the duration from the beginning of the reaction to the gel point) for the reaction was much shorter when the gelation temperature was increased (Fig. 1). To deterTable 1. The effects of reaction conditions on the density of the AG-IPA and the corresponding CA-IPA [a]. mine the effect that the reaction conditions (i.e., temperature, concentration, cure time) Aging Aging Density of Density Samples R-F Gelation duration AG-IPA of CA-IPA[b] No. content temperature temperature have on the physical properties of the aero[oC] [h] [g/cm3] [g/cm3] [%] [oC] gels, we prepared a variety of samples by this AG-12 26.2 20 75 72 0.73 0.88 new method, and the results are listed in TaAG-16 26.2 20 70 90 0.89 ble 1. From these results, it can be seen, not AG-17 16.7 20 70 90 0.88 surprisingly, that we can control the densities AG-21 [c] 26.2 20 70 90 0.53 AG-52 16.7 40 75 69 0.48 0.66 of the resulting aerogel by changing the mass AG-53 16.7 50 75 69 0.45 0.61 content of the resorcinol and furfural used in AG-54 16.7 50 75 69 0.45 the reaction. In addition, the data show that AG-56 16.7 60 75 69 0.44 0.57 AG-57 16.7 70 75 69 0.41 0.48 as the gelation temperature increases, the AG-58 26.2 60 75 50 0.57 0.75 densities of the organic aerogels (denoted AG-59 11.5 60 75 50 0.31 0.42 AG-IPA) samples and related carbon aeroAG-60 5.9 60 75 50 0.17 0.23 AG-61 26.2 70 75 50 0.34 gels (denoted CA-IPA) samples decrease. AG-62 11.5 70 75 50 0.28 0.32 Using this method, we can prepare organic AG-63 5.9 70 75 50 0.13 0.15 aerogels with densities ranging from 0.13 to [a] All aerogels were prepared with 1 % HCl as a catalyst with the exceptions of AG-16 (0.2 %), AG0.57 g/cm3 and carbon aerogels with densities 17 (0.2 %), and AG-21 (0.8 %). [b] Carbonization was performed at 800 C under N2 atmosphere. ranging from 0.15 to 0.75 g/cm3. We have also [c] Dried using supercritical carbon dioxide.

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determined that the mass content of the reactants and the amount of HCl used affects the gelation time (Figs. 2,3). It can be seen that the gelation time decreased when the mass content of the reactants or the amount of HCl used was increased.

gen adsorption/desorption techniques to obtain more detailed information on the pore size distribution of the CA-IPA samples, and the results will be reported in a future paper.

2.3. Transport Properties 2.2. Textural Properties of the Carbon Aerogels Transmission electron microscopy (TEM) was utilized to examine the morphology of the organic and carbon aerogels (Fig. 4). The TEM observations show that the texture of the aerogels processed in supercritical isopropanol is similar to those of aerogels prepared by the carbon dioxide supercritical drying method.[57,15] The carbon framework of the CA-IPA samples consists of interconnected carbon nanoparticles that are typically 2030 nm in size. There is no apparent difference in the particle size for the various CA-IPA samples prepared under different conditions. The interconnected particles define the meso- and micropores present in the carbon framework. The surface areas for the carbon aerogels were measured using nitrogen adsorption/desorption techniques (Table 2). The results show that all of the CA-IPA samples have high Brunauer EmmettTeller (BET) surface areas ranging from 557 to 656 m2/g. The total surface area of the CA-IPA is a sum of the micropores inside the carbon nanoparticles and the external surface of the carbon nanoparticles. For the CA-IPA, the external surface area of the nanoparticles constitutes 4142 % of the total surface area because the CA-IPA samples are packed with many carbon nanoparticles. The surface areas of the aerogels increase slightly with decreasing mass density for CA-IPA samples prepared at the same gelation temperature. We are currently using scanning electron microscopy (SEM) and nitroTable 2. Textural properties of the CA-IPA materials. Sample Gelation No. temperature [oC] CA-59 CA-60 CA-57 CA-62 CA-63 60 60 70 70 70 Density of CA-IPA [g/cm3] 0.42 0.23 0.48 0.32 0.15 BET area [m2/g] 615 630 557 584 656 Micropore area [m2/g] 357 362 328 338 389 External surface area [m2/g] 258 268 229 246 267

The experimental results of the temperature-dependent magnetic susceptibilities of three representative CA-IPA samples are shown in Figure 5. The data show that the temperature-dependent magnetic susceptibilities of the samples follow
6.0x10
-5

Susceptibility (emu/g)

4.0x10

-5

2.0x10

-5

CA-60 CA-57 CA-52

0.00 0.05 0.10
-1

0.0

0.15

0.20

1 / T (K )
Fig. 5. Temperature dependence of the magnetic susceptibility for the CA-IPA samples.

a Curie behavior in the low temperature region (below 45 K), which is similar to the behavior of carbon aerogels prepared by traditional methods.[6] The spin concentrations (N) for these CA-IPA samples were calculated based on the Curie constants obtained from the curve-fitting results (Table 3).[6] We found that the spin concentrations of the CA-IPA samples increase as
Table 3. The spin concentration of the CA-IPA samples. Sample Mass density [g/cm3] N [1019 spins/g] CA-52 0.66 1.053 CA-57 0.48 1.235 CA-60 0.23 4.200

(a)

(b)

(c)

100nm

100nm

Fig. 4. TEM images of the CA-IPA samples. a) CA-57. b) CA-59. c) CA-60.

their mass density decreases. This same trend has been reported for traditional carbon aerogels.[6] The resistivities of the samples increase as the temperature decreases, especially at low temperature (Fig. 6). At the same time, the resistivities of the samples also decrease with a decrease in the mass density. As expected, a linear behavior on a log r vs. (1/T)1/2 plot can be obtained for the CA-IPA samples (Fig. 7), indicating that the conduction of these materials still obeys a tunneling and/or hopping mechanism, similar to that seen in traditional aerogel materials.[6] In addition, we observed that the resistivities of the CAIPA samples greatly depend on the carbonization temperature. It can clearly be seen that the resistivities of the CA-IPA samples 100nm greatly decrease when the carbonization temperature increases (Figs. 8,9). The resistivity

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10

Resistivity (Ohms-cm)

10

0.32 g/cm

Log

CA-57 (800 C)
2

10

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0 50 100 150
3

CA-57 (850 C)
0

10

CA-57 (900 C)
200 250 300

0.0

0.1

0.2

Temperature (K)

1/T

1/2

0.3

0.4

Fig. 6. Temperature dependence of the resistivity of the CA-IPA samples with different densities.

Fig. 10. Temperature dependence of the resistivity of CA-IPA-57 samples carbonized at different temperatures plotted as log r vs. 1/T1/2.

0.32 g/cm
4

Log

CA-62 (800 C)

0.15 g/cm
2

Log

0.48 g/cm

CA-62 (850 C)
0

0 0.0

CA-62 (900 C)
0.1 0.2 0.3
1/2

0.1

0.2

1/T

1/2

0.3

0.4

0.0

0.4

1/T

Fig. 7. Temperature dependence of the resistivity of the CA-IPA samples with different densities.

Fig. 11. Temperature dependence of the resistivity of CA-IPA-62 samples carbonized at different temperatures plotted as log r vs. 1/T1/2.

10

Resistivity (Ohms-cm)

10

10

CA-57 (800C) CA-57 (850C) CA-57 (900C)

0 50

10

of the CA-IPA samples is most sensitive to the carbonization temperature when it is around 850 C. The resistivities of the CA-IPA samples drop by a factor of ~ 103 at 10 K and by a factor of ~ 102 at 300 K when the carbonization temperature increases from 800 C up to 850 C. Though the resistivities of the CA-IPA samples are greatly changed over the range of carbonization temperatures from 800 C to 900 C, all of the samples show a linear behavior in log r vs. (1/T)1/2 (Figs. 10,11).
250 300

10

-2

Temperature (K)

100

150

200

3. Conclusions
In this report, we describe a new method for the fabrication of carbon aerogels (CA-IPA) that is potentially faster and easier than traditional methods. In this process, resorcinol and furfural are polymerized in isopropanol using HCl as a catalyst. The resulting alcogels are dried directly using supercritical isopropanol to afford organic aerogels that can then be carbonized under a nitrogen atmosphere. This process can be used to prepare organic and carbon aerogels over a wide range of densities. The framework of the CA-IPA samples consists of interconnected carbon nanoparticles with diameters of 2030 nm. As a result, these materials exhibit relatively high internal surface areas (557656 m2/g). The temperature-dependent magnetic susceptibilities of the CA-IPA samples fit the Curie law in the low temperature region. The spin concentrations of the CA-IPAs increase as the mass densities of the materials de-

Fig. 8. Temperature dependence of the resistivity of CA-IPA-57 samples carbonized at different temperatures.

Resistivity (Ohms-cm)

10

10

CA-62 (800 C)
10
1

CA-62 (900 C) CA-62 (850 C)

o

10

-1

50

100

150

200

250

300

Temperature (K)
Fig. 9. Temperature dependence of the resistivity of CA-IPA-62 samples carbonized at different temperatures.

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crease. The electrical conduction of the CA-IPA samples obeys a tunneling and/or hopping mechanism. The transport properties of the CA-IPA materials are similar to those of CA samples prepared by traditional methods. It was determined that the resistivities of the CA-IPA samples are highly sensitive to the carbonization temperature, but the conduction mechanism of the CA-IPA samples does not change for the samples carbonized in the range of 800900 C.

For measurement of the electrical resistivity, the samples were shaped into a cube of dimensions 3.5 mm 3.5 mm 1.0 mm and silver paint was used to establish the contacts. The currentvoltage data were taken with a digital current source and a digital nanovolt meter attached to a Quantum Design magnetometer, and the resistivity was calculated by the van der Pauw method [18]. Received: October 31, 2003 Final version: April 15, 2003

4. Experimental
Synthesis of Organic Aerogels: Organic gels were synthesized by dissolving resorcinol and furfural (with molar ratio 1:2) in isopropanol in a vial, heating the vial to a certain temperature in an oil bath for 30 min after adding an appropriate amount of HCl as a catalyst, and sealing the vial to polymerize its contents, followed by aging at 75 C for 25 days. The monolithic organic gels were then transferred into a pressure vessel and dried in supercritical isopropanol by heating the contents of the autoclave from 25 C to 265 C for 3 h, then maintaining the temperature at 265 C for 25 min. The resultant organic aerogels are denoted as AG-IPA. Carbonization of the aerogel monoliths was performed with a quartz tube furnace at 800900 C for 3 h under an N2 atmosphere. The carbon aerogels are denoted as CA-IPA. The bulk densities of these aerogels were determined by measuring the dimensions and mass of each sample. The gel point was determined by visually observing the phase transition from a liquid to a solid for the reaction system. Physical Characterization: The surface area determination was performed by the BET method using an ASAP 2000 Surface Area Analyzer (Micromeritics Instrument Corporation). Samples of approximately 0.1 g were heated to 200 C to remove all adsorbed species. Nitrogen adsorption data were then taken at relative pressures (P/P0) from 0.05 to 0.25 at 77 K to calculate the surface area by BET theory [17]. Some powders were scraped from the resulting bulk samples and dispersed in water onto a copper grid for microscopic examination. The structures of the CA-IPA samples were observed by transmission electron microscopy, using model JEM 2000FX instruments. Magnetic susceptibility measurements were carried out in a Quantum Design magnetometer. Samples were mounted in drinking straws and scanned in the temperature range 4300 K. The magnetic susceptibility was calculated according to the following formula: v M H m (1) [1] R. W. Pekala, J. Mater. Sci. 1989, 24, 3221. [2] R. W. Pekala, C. T. Alviso, F. M. Kong, S. S. Hulsey, J. Non-Cryst. Solids 1992, 145, 90. [3] R. W. Pekala, C. T. Alviso, J. D. LeMay, in Chemical Processing of Advanced Materials (Eds: L. L. Hench, J. K. West), John Wiley & Sons, New York 1992, p. 671. [4] F. M. Kong, J. D. LeMay, S. S. Hulsey, C. T. Alviso, R. W. Pekala, J. Mater. Sci. 1993, 8, 3100. [5] R. W. Pekala, F. M. Kong, J. Phys., Colloq. 1989, C4, 33. [6] A. W. P. Fung, Z. H. Wang, K. Lu, M. S. Dresselhaus, R. W. Pekala, J. Mater. Res. 1993, 8, 1875. [7] Y. Hanzawa, K. Kaneko, N. Yoshizawa, R. W. Pekala, M. S. Dresselhaus, Adsorption 1998, 4, 187. [8] M. Hosoya, G. Reynolds, M. S. Dresselhaus, R. W. Pekala, J. Mater. Res. 1993, 8, 811. [9] K. L. Yang, T. Y. Ying, S. Yiacoumi, C. Tsouris, E. S Vittoratos, Langmuir 2001, 17, 1961. [10] R. W. Pekala, J. C. Farmer, C. T. Alviso, T. D. Tran, S. T. Mayer, J. M. Miller, B. Dunn, J. Non-Cryst. Solids 1998, 225, 74. [11] R. Saliger, U. Fischer, C. Herta, J. Fricke, J. Non-Cryst. Solids 1998, 225, 81. [12] C. Moreno-Castilla, F. J. Maldonado-Hodar, J. Rivera-Utrilla, E. Rodriguez-Castellon, Appl. Catal. A 1999, 183, 345. [13] M. W. Droege, US Patent 5 945 084, 1999. [14] R. W. Pekala, US Patent 4 873 218, 1989. [15] R. W. Pekala, C. T. Alviso, X. Lu, J. Gross, J. Fricke, J. Non-Cryst. Solids 1995, 188, 34. [16] A. Gardziella, L. A. Pilato, A. Knop, Phenolic Resins: Chemistry, Application, Standardization, Safety and Ecology, Springer, New York 1999. [17] S. J. Gregg, K. S. W. Sing, Adsorption, Surface Area, and Porosity, 2nd ed., Academic Press, London 1982. [18] L. J. van der Pauw, Philips Res. Rep. 1958, 13, 1.

where v is the magnetic susceptibility, M is the magnetization in units of emu, H is the magnetic field in units of G, and m is the mass in grams.

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