Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2013.

Supporting Information

for Adv. Mater., DOI: 10.1002/adma.201204530

Ultralight and Highly Compressible Graphene Aerogels

Han Hu, Zongbin Zhao,* Wubo Wan, Yury Gogotsi, and

Jieshan Qiu*
 Submitted to
DOI: 10.1002/adma.201204530

Supporting information for

Ultralight and Highly Compressible Graphene Aerogels

Han Hu a, Zongbin Zhao a, *, Wubo Wan a, Yury Gogotsia,bJieshan Qiu a ,*,

a
Carbon Research Laboratory, Liaoning Key Lab for Energy Materials and Chemical
Engineering, State Key Lab of Fine Chemicals, School of Chemical Engineering, Dalian
University of Technology, Dalian 116023, China
b
Department of Materials Science and Engineering and A.J. Drexel Nanotechnology Institute,
Drexel University, Philadelphia, Pennsylvania 19104, USA
* To whom correspondence should be addressed. zbzhao@dlut.edu.cn(Z.B. Zhao),
jqiu@dlut.edu.cn (J.S. Qiu)

1. Experimental detail

Synthesis of ultralight graphene aerogels (ULGA)

Graphite oxide was prepared via a modified Hummers method reported elsewhere.[1] The
synthesis process of the reduced graphene aerogel is illustrated in Figure 1a. Typically,
ethylenediamine (20 L) was added into graphene oxide dispersion (3 mg mL-1, 5ml). The
mixture was sealed in a glass vessel and heated for 6 h at 95 oC for synthesis of functionalized
graphene hydrogel (FGH). After freeze-drying for 48 h, the solvent within the hydrogel was
completely removed and the functionalized graphene aerogel (FGA) was produced. Then, the
aerogel was loaded into a quartz tube (30 cm in length, 18 mm in diameter) and flushed with
argon (100 mL min-1) for 20 min to remove air. After that, the FGA was heated with
microwaves (800 W) for 1min, giving rise to the final ULGA.
Characterizations and mechanical tests

Elemental analysis was conducted by Elemental Analyzer Vario EL III. The X-ray
diffraction (XRD) patterns were recorded on a Rigaku D/Max 2400 diffractometer. Surface
functional groups were studied using a Nicolet-20DXB Fourier transform infrared
spectrometer (FTIR). Scanning electron microscopy (SEM) of monolith structures was
performed using a QUANTA 450 microscope. The transmission electron imaging of ridges
structure was obtained on FEI TF30 transmission electron microscopy (TEM) at 300 KV. The
XPS were recorded on ESCALAB MK II X-ray photoelectron spectrometer. The Raman
analysis was carried out on RENISHAW inVia Raman Microscope with 633 nm excitation
wavelength.

The compressive test was performed on the equipment shown in Figure S1. The injection

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pump (TJ-3A/W0109-1B, Baoding Longer Precision Pump Co., Ltd.) drives the compression
head up and down at a preset speed. The load on the sample was recorded using a pressure
sensor.

Figure S1. Schematic illustration of equipment for the compressive test

2. Factors influence the volume of gel

The volume of chemically converted graphene gel is highly dependent on the

concentration of GO in the solution[2] and stability of nanosheets which is determined by pH
value in the aqueous phase. [3] Therefore, influence of concentration and pH on the volume of
gel was investigated in detail.

Figure S2. The influence of GO concentration on the volume of hydrogel.

GO dispersions with concentrations ranging from 1~5 mg mL-1 were chosen. As shown in
Figure S2, an integrated hydrogel structure cannot form at concentrations lower than 2 mg
mL-1. When the concentration of GO is higher than 3 mg mL-1, an almost shrinkage-free
hydrogel can be produced. It was found that the density of FGA increases with the
concentration of GO; therefore, for producing aerogel with the lowest density, a GO
dispersion with concentration of 3 mg mL-1 was used in this study.
The stability of GO in aqueous phase mainly results from the carboxylic acid groups and
the most suitable pH value for the dispersion of GO is around 10-12. As shown in Figure S3,
the addition of 40 L EDA into 5 mL of GO dispersion with a concentration of 3 mg mL-1
causes the pH to increase up to 12 and results in the volume shrinkage of the aerogel. On the
other hand, the additive of 20 L EDA can produce the aerogel with negligible volume
shrinkage as well as a smooth surface. Thus, the amount of EDA was fixed at 20 L.

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Figure S3. (a) The pH value after adding EDA into the GO solution. (b) The comparison of
volume of graphene aerogels reduced with different amounts of EDA; the numbers in the
figure represents the amount of EDA (L) added.

3. Graphene hydrogels from other chemical reduction approaches

For comparison, graphene hydrogels from other chemical reduction approaches were also
fabricated. The L-ascorbic acid (L-AA),[4] NaHSO3,[5] N2H4 and hydrothermal[6] mediated
reduction methods were employed. In all four methods, 5 mL GO dispersion with
concentration of 3 mg mL-1 is used. Except for the hydrothermal approach, the other three
methods proceed for 6 h at 95 oC and the amounts of reducing agents are 45 mg, 20 mg and
20 L for L-ascorbic acid, NaHSO3 and N2H4, respectively. While in the hydrothermal
method, GO dispersion was sealed in a 10 mL autoclave and heated for 12 h at 180 oC. The
comparison of graphene hydrogels from different approaches is shown in Table S1. Due to
strong bubbling during the N2H4 mediated reduction process, the hydrogel was broken into
pieces and the volume of gel was not measured. GO is listed on the left for reference.
Samples are represented by names of reducing agents or assembly methods.

Table S1 Volume comparison of graphene hydrogels via different approaches

Samples
GO EDA NaHSO3 L-AA Hydrothermal N2H4
Volume [mL] 5.0 4.3 1.2 1.6 1.5 N/A
Volume
0 14% 76% 68% 70% N/A
shrinkage [%]

4. Wettability estimation of aerogels produced by different methods

The aerogels show different permeation time for water droplets due to different wettability.
[7]
The droplet can be driven into the pores more rapidly with a hydrophilic surface and vice

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verse. As shown in Figure S4, the time for droplet to permeate into pores of aerogel is 120 ms
for graphene oxide aerogel, 75 s for NaHSO3-reduced graphene aerogel, 50 s for L-AA-
reduced graphene aerogel, 6 s for EDA-reduced graphene aerogel. Thus the droplet shows the
fastest permeation velocity in EDA-reduced graphene monolith among reduced graphene
aerogels, indicative of the most hydrophilic surface.

Figure S4. The permeation of droplets into GO aerogel (a), NaHSO3-reduced graphene
aerogel (b), L-ascorbic acid-reduced graphene aerogel (c) and EDA-reduced graphene aerogel
(d)

Figure S5. FTIR spectra of graphene samples during the EDA-mediated assembly showing
time-dependent variation of surface functional groups

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Figure S6. Schematic illustration of mechanism of EDA-mediated functionalization and

reduction of GO, the restored sp2 regions are marked with red line.

Figure S7. TEM images of curved ridges or crumples and stacked structure on ULGA

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Figure S8. Time-dependent variation of nitrogen content during MWI

4. Variation of properties from GO to ULGA

Figure S9. (a) Raman spectra, (b) FTIR and (c) electrical conductivity of GO, FGA and
ULGA

During the transformation process, the surface of GO firstly shows disappearance of some
oxygen-containing groups accompanying by the appearance of nitrogen-containing groups.
After the MWI treatment, most of the functional groups are driven to flee, leaving ULGA with
high carbon content (Figure S9b). Besides, GO is electrically insulated while both FGA and
ULGA show conductivity of 6.910-4 and 2.510-2 S cm-1, respectively (Figure S9c). he
conductivity of ULGA is two orders of magnitudes higher than that of FGA.

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Figure S10. Digital image of two ULGA samples rested on a dandelion.

Figure S11. The density of graphene aerogels. (a) The density of aerogels from different
approaches before and after MWI. (b) The density of aerogels from EDA-mediated reduction
both before and after MWI as a function of GO concentration (mg mL).

5. Calculation of the porosity of the aerogel

The porosity is calculated based on the followed equation:[8]

=1-/o
where represent the porosity, is the density of the as prepared graphene aerogel while o is
the density of graphite which is assumed to be 2.2 g cm-3.

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Figure S12. Compressibility of graphene aerogels produced from L-AA (a,b) and NaHSO3
mediated (c, d) reduction before (a,c) and after (b, d) MWI.

Graphene aerogels produced from L-ascorbic acid (L-AA) and NaHSO3-mediated

reduction also can partially recover after compression. However, the aerogels after MWI
show irreversible deformation or collapse under loading (Figure S12).

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6. The stress-strain curves of aerogels produced by different methods.

Figure S13. The stress-strain curves of aerogels from different methods. The stress-strain
curves of graphene aerogel from L-AA -mediated reduction approach (a), NaHSO3-mediated
reduction approach (b) as well as EDA-mediated reduction approach (c) before and after
MWI

All samples were compressed at speed of 1 mm min-1 to strain of 50%. The stresses during
the compression process for aerogels after MWI are different from the original ones. Thus,
relative stresses were plotted in Figure S13. The positions where the stress reaches zero
during the unloading process are marked by the arrows in this figure. As shown in Figure S13,
the aerogels obtained from L-AA and NaHSO3-mediated reduction have irreversible
deformation of 42% and 35% under the strain of 50%. The MWI can only reduce the
irreversible deformation from 42% and 35% to 37% and 20%, respectively, while the
irreversible deformation can be reduced from 39% for FGA to almost 0 for ULGA under the
same strain.

Figure S14. SEM images of loading and unloading states of ULGA under compression

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Figure S15. Strain-stress curves of ULGA with compression lasting for 1000 cycles.

References
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[5] L. F. Yan, W. F. Chen, Nanoscale 2011, 3, 3132.
[6] Y. X. Xu, K. X. Sheng, C. Li, G. Q. Shi, ACS Nano 2010, 4, 4324.
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[8] Y. Liu, W. Qian, Q. Zhang, A. Cao, Z. Li, W. Zhou, Y. Ma, F. Wei, Nano Lett. 2008, 8,
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