Carbon aerogel as active material for double layer capacitor:

synthesis and electrochemical characterization

Natalia A. Caasa, Dong-Won Parka, Marina Schwanb, Barbara Milowb,
Lorenz Ratkeb, K. Andreas Friedricha
a

German Aerospace Center (DLR), Institute of Engineering Thermodynamics, Stuttgart, Germany.

b
German Aerospace Center (DLR), Institute of Materials Research, Cologne, Germany.

Rsum
Carbon aerogels (C-aerogels) are highly porous materials
produced by carbonization of resorcinol-formaldehyde
aerogels under inert atmosphere. Carbon aerogel-based
electrodes were electrochemically characterized for
supercapacitor applications. The surface area and pore
sized distributions of the C-aerogel as the electrode active
material affects drastically the capacitance behavior.
Through the galvanostatic charge/discharge measurement,
it was found that the supercapacitor with mesoporous Caerogel showed the best performance after 10000 cycles,
reaching capacitance values of 17.6 and 19 Fg1 for
current densities of 2 and 40 Ag1, respectively.

Introduction
Electrical double layer capacitors (EDLCs), also known as
supercapacitors, are today considered as one of the most
significant electrochemical storage systems. Contrary to
batteries supercapacitors are not restricted by the
electrochemical charge transfer and therefore can be
operated at high charge and discharge rates [1]. Among of
the various materials, C-aerogels are promising candidates
for supercapacitors because of its large specific area, high
electrical conductivity, chemical stability, lower cost, and
wide operating temperature range [2][3]. Furthermore, a
high surface area but also simple and industrially scalable
fabrication methods are important for the application of Caerogels as active material in supercapacitors.
In this work, C-aerogels with different morphologies, such
as particle and pore size, and physical properties were
synthesized and prepared as an electrode active material.
Moreover, electrochemical characterization was carried
out to evaluate the influence of the structural
characteristics on the performance of EDLCs.

for all three solutions at room temperature with stirring

velocity of 250 rpm with a cross magnetic stirring bar. The
homogeneous, transparent solutions were placed in
sealable polypropylene containers at 80 C in an oven.
During gelation and curing the gel became dark-brown.
After four days CA-1 and CA-2 gels were dried one day at
80 C in a drying cabinet. The curing of CA-3 took place
seven days at the same temperature. After aging, the gel
CA-3 was washed with acetone six times and then dried
with supercritical carbon dioxide in an autoclave from
Eurotechnika (Germany). The dried RF aerogels were
pyrolized. The pyrolysis was carried out in an electric
furnace (Standardofen F(A), Gero Hochtemperaturofen
Ltd., Germany). The RF aerogels were placed in the
furnace and after purge three times with argon, heated to
the carbonization temperature of 1000 C. The heat rate
was adjusted to 6-7 Kmin-1, the argon passed in furnace
with a pressure of 4 bars. The samples were maintained on
these conditions for 60 minutes and then cooled down to
the room temperature in flowing argon. The CA-1 sample
was milled with a cross beater mill (SK100, RETSCH
GmbH, Germany) and CA-2 and CA-3 with ball mill
(Pulverisette 7, BJ 2006 von Fritsch, Germany).
Fig. 1 shows the SEM images of the different C-aerogel
powders.

Experimental work
Synthesis of C-aerogels
Resorcinol (R) was dissolved in deionized water (W) at
room temperature (20-22 C) with molar ratio
R:W = 0.044 for CA-1 and CA-2 and with R:W=0.009 for
CA-3. Then aqueous solution of formaldehyde (F) and
sodium carbonate (Cat) were added under stirring. The
molar ratio for CA-1 and CA-2 was R:F=0.74 and for CA3 0.5. The amount of sodium carbonate was for CA-1 and
CA-2 identical R:C=1500 and for CA-3 R:C=50. After 5
minutes stirring the pH of solutions CA-1 and CA-2 was
adjusted to 5.5 with 2 N nitric acid. The solution of CA-3
was not modified. The stirring was continued for 30 min

Figure 1. SEM images of different C-aerogels.

Electrode preparation
The electrodes consisted of 90 wt% syn. C-aerogel (DLR,
Cologne), 5 wt% carbon black (Super P, Alfa Aesar) as
conductive additive, and 5 wt% of carboxymethylcellulose

(CMC, Aldrich) as binder. CMC was dissolved in water

and mixed with the solid components in a roller mixer for
12 h. The slurry was coated over an aluminium foil (20 m
thick) using a tape casting machine (velocity of coating
12 mms1). The coated electrode was dried at room
temperature for 5 h and then at 80 C in a vacuum oven for
12 h. Finally, the loading of the layer was ~ 0.7 mgcm2.
The electrochemical performance of the EDLC was
characterized using Swagelok-type cell. A glass fiber
separator (Whattmann G/F, 0.67 mm thick, 12 mm
diameter) immersed in 40 L electrolyte was placed
between the electrodes (10 mm diameter). As electrolyte
1 M tetraethylammonium tetrafluoroborate (Et4NBF4,
Aldrich) in propylene carbonate (PC, Aldrich) was used.

Potential / V

Current density / Ag-1

2
10
4
40
8
3

1st cycle

Results and discussion

Current density / Ag -1

4
3

Scan rate / mVs-1

10
20
50

100
200

10

15

20

25

30

35

Time / s

Figure 3. Charge-discharge curves at different current

densities.
26

-1

Current density / Ag-1

2
10
24
4
40
8

Capacitance / Fg

C-aerogels consisted of large particles about 1-3 m (CA-1

and CA-2) showed very low capacitance behavior. This is
attributed to the lower specific surface and lower volume
of mesoporous compared with sample (CA-3). Thus, the
electrolyte may not penetrate in the nano-pores of the
microspheres, reducing the specific area available for
electrode-electrolyte interface.
Cyclic voltammetry was performed at various scan rates
for the EDLC (C-aerogel: CA-3, see Fig. 2). The shape of
the curves is characteristic for capacitive behavior and
capacitance near to 25 Fg1 was achieved at the lowest Crate.

22
20
18
16

14

500

1000 1500 2000 2500 3000

Cycle / #

-1

Figure 4. Capacitance of EDLC (C-aerogel: CA-3. The

coulombic efficiency is ca. 100% in all the cases.

-2

Conclusions

-3
0.0

0.5

1.0

1.5

2.0

2.5

3.0

Potential / V

Figure 2. Cyclic voltammetry of EDLC (C-aerogel: CA-3)

at different scan rates.
In Fig. 3 the results of the galvanostatic charge-discharge
test for the first cycle are shown for different current
densities (240 Ag1), in an operating voltage of 2.7 V.
The evolution of capacitance over 3000 cycles is displayed
in Fig. 4. At high current densities, the capacitance is
stable after 250 cycles and remains constant (~ 17.5 Fg1)
up to the 3000 cycle. With decreasing current density, high
capacitance is reached and capacitance retention higher
than 90% is obtained after 3000 cycles (at a current density
of 2 Ag1). The coulombic efficiency is stable, reaching
almost 100 % for all cycles.
Further chronopotentiometric tests up to 10000 cycles
showed capacitance values of 17.6 and 19 Fg1 for current
densities of 2 and 40 A g1, respectively.

C-aerogel synthesized from resorcinol-formaldehyde

aerogel is a suitable and promising material for EDLS due
to the high specific capacitance and capacitance retention.
Additional modifications and improvements on C-aerogel
synthesis (for example, surface activation), electrode
fabrication, and electrolyte composition may further
enhance the performance of the EDLCs.

References
[1]

[2]

[3]

Y. Zhu, S. Murali, M.D. Stoller, K.J. Ganesh, W.

Cai, P.J. Ferreira, A. Pirkle, R.M. Wallace, K.A.
Cychosz, M. Thommes, D. Su, E.A. Stach, R.S.
Ruoff, 332 (2011) 1537.
R.W. Pekala, J.C. Farmer, C.T. Alviso, T.D. Tran,
S.T. Mayer, J.M. Miller, B. Dunn, J. Non. Cryst.
Solids 225 (1998) 74.
A.G. Pandolfo, A.F. Hollenkamp, J. Power
Sources 157 (2006) 11.