Front. Mater. Sci.

2012, 6(2): 176182

DOI 10.1007/s11706-012-0166-4

COMMUNICATION

Exfoliation and dispersion of graphene in ethanol-water

mixtures

Wei-Wei LIU1, Bao-Yu XIA1, Xiao-Xia WANG2, and Jian-Nong WANG ()3
1 Shanghai Key Laboratory for Laser Processing and Materials Modication, School of Materials Science and Engineering,
Shanghai Jiao Tong University, 800 Dong Chuan Road, Shanghai 200240, China
2 School of Materials Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092, China
3 Key Laboratory of Safety Science of Pressurized System (Ministry of Education), School of Mechanical and Power Engineering,
East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China

Higher Education Press and Springer-Verlag Berlin Heidelberg 2012

ABSTRACT: Graphene has attracted much attention as a new nano-carbon for its
unique structure and properties. However, production and dispersion of unfunctionalized
graphene are still big challenges. Herein, we demonstrate a simple method for
preparation and dispersion of such graphene with low cost and non toxicum. This
approach is achieved by exfoliating graphite in an ethanol/water mixture and forming
stable dispersion of mono- and few-layer graphenes. The ratio of ethanol/water in the
mixture is found to be crucial to both the exfoliation and dispersion processes. Exfoliation
in pure water or pure ethanol produces no graphene. This method avoids the
conventional use of harsh oxidants and surfactants; therefore, the graphitic structure
is well maintained without destruction. Beneting from the use of ethanol and water, it can
be easy to prepare transparent and conductive graphene lms by vacuum ltering or
spray method, and does not need special post-treatment to remove the impurity, which
could be benecial for potential applications in electronic, optic and energy areas.

KEYWORDS: graphene, liquid-phase exfoliation, transparent conductive lm, solubility

parameter

Graphene, a two-dimensional lattice of carbon with a
thickness of only one single atom [13], has attracted
signicant attention as a result of its outstanding electronic,
mechanical, and chemical properties, and could have wide
applications for transparent conductive lms, supercapaci-
tors, transistors, sensors, and catalyst supports [49].
The most common approach to produce graphene is
exfoliation graphene oxide (GO) from graphite oxidation
followed by reduction to get reduced graphene oxide (rGO)
Received March 15, 2012; accepted April 7, 2012
E-mail: jnwang@ecust.edu.cn
[1014]. However, the graphitic structure was destructed
during the oxidation process and cannot be fully restored
[1516]. Moreover, rGO is prone to aggregation owing to
its hydrophobic nature, and thus, surfactants or strong
capping molecules must be introduced to improve the
dispersibility of graphene. Nevertheless, such surface
ligands are difcult to be removed and will disrupt the
electrical structure of graphite [1013].
Recently, another liquid-phase method, without oxida-
tion, intercalation and reduction, was introduced by direct
exfoliation of graphite in a certain solvent and formation of
graphene in solution. Some solvents and surfactant/solvent
mixtures have been shown positive results for exfoliation
 Wei-Wei LIU et al. Exfoliation and dispersion of graphene in ethanol-water mixtures
and dispersion of graphene [11,1722], However, these
solvents are usually expensive, toxic and difcult to
remove because of their high boiling points; and their
residues in the nal samples are certainly detrimental to the
expected excellent properties of graphene [21,2328].
Here, we report a liquid-phase exfoliation method based
on the mixture of ethanol and water. We demonstrate that
graphite akes can be exfoliated and the resultant graphene
sheets can be well dispersed in the mixture without
addition of any surfactants. The fraction of ethanol in the
mixture was found to be crucial to both the exfoliation and
dispersion. For the mixtures with 5080 vol.% ethanol, the
graphene dispersion with a maximum concentration of
0.05 mg/mL was achieved. The obtained graphene disper-
sion was stable for years without the usage of any
surfactants. Moreover, beneting from the use of ethanol
and water, it can be easy to prepare transparent and
conductive graphene lms by vacuum ltering or spray
method, and does not need special post-treatment to
remove the impurity, which could be benecial for
potential applications in electronic, optic and energy areas.
The typical procedure for preparing graphene started
with the addition of graphite akes in a mixed solution of
ethanol and water. The graphite initial concentration was
5 mg/mL, and the ethanol concentration in the mixed
solution was varied from 0 to 100 vol.%. The solution
contained in a cylindrical vial (100 mL) was sonicated in a
sonic bath for 90 min. After the resultant dispersion was
centrifuged at 3000 rpm for 60 min, the supernatant was
decanted by pipetting off the upper half of the dispersion
for further use.
Graphene lms were prepared by a ltering method
[17,2930]. A certain volume of the graphene dispersion was
ltered through a mixed cellulose ester (MCE) membrane
with an average pore size of 0.2 m. Then, the graphene lm
with the attached MCE membrane was wetted with deionized
water and put on a glass substrate. The membrane, which was
now on the top of the lm, was covered with several pieces of
porous paper and a at plate. This was to apply a
compressive load to keep the lm at as it underwent
drying. After oven drying in air at 90C for 3 h, the load was
removed and the membrane was dissolved using acetone,
leaving a graphene thin lm on the substrate.
Transmission electron microscopy (TEM) was used for
analyzing the morphology and microstructure of the
prepared graphene samples. TEM images and selected
area electron diffraction (SAED) patterns were taken by
using a microscope of JEM-2010 (JEOL Ltd., Japan)
177
operated at 200 kV. The specimens for TEM were prepared
by drop casting the graphene dispersion onto a holey
carbon-coated copper grid and subsequent drying under
ambient condition. Atomic force microscopy (AFM)
images of graphene were taken on a commercial scanning
probe microscope with a Nanoscope IIIa controller under
tapping mode (Digital Instruments, Multimode 3000,
USA). Commercial silicon cantilevers were used (Nano-
sensors, Type NCL-100) with a resonance vibration
frequency of ~330 kHz. The samples were made by casting
the graphene dispersions onto freshly cleaved mica
substrates and drying under ambient condition. Absor-
bance measurements for graphene dispersion and graphene
lms were performed using a Nicolet Evolution 300 UV-
Visible Spectrophotometer (Thermo Fisher Scientic Inc.,
USA). The contributions from the ethanol/water solvent
and optical cuvette were subtracted from the spectra of the
graphene dispersions. Similarly, for graphene lms, the
contribution from the glass substrate was subtracted from
the spectra of the transparent conducting graphene lms.
The absorbance coefcient was collected from 6 different
dispersions. For each of the dispersions, the graphene
solubility was measured by ltering a large volume of the
graphene dispersion through a pre-weighted polyvinyli-
dene uoride (PVDF) lter. By taking a cell length of 1 cm
into account, the average absorbance coefcient was
determined to be 3182 L$g1$m1 (660 nm). Sheet resisti-
vity was measured by a 4-point probe (NHY Co., SD-510),
and three different sites of each sample were measured to
get an average value.
Graphene dispersions were prepared by bath sonication
of natural graphite akes in ethanol/water mixtures.
Representative TEM images are illustrated in Figs. 1(a)
and 1(b). Few-layer and mono-layer graphenes with no
visible evidence of large-scale defects are observed. This is
further supported by the SAED result shown in Fig. 1(c).
The diffraction pattern, with the typical six-fold symmetry
expected for graphite/graphene, is labeled by the Miller-
Bravais (hkil) indices. The intensity ratio of I{1100}/
I{2110} > 1 conrms that the graphene ake is of monolayer
[23,28,31]. Furthermore, the graphene akes, recognized
as monolayers with a thickness of ~0.7 nm [32], can also be
seen in the AFM images (Fig. 1(d)).
To determine the concentration of graphene in an
ethanol/water mixture, we measured the UV-vis absor-
bance of the solution (Fig. 2(a)) based on Lambert-Beer
law that has been widely used to quantify the amount
of graphene dispersed in a solution [11]. As shown in
178 Front. Mater. Sci. 2012, 6(2): 176182

Fig. 1 (a)(b) Bright-eld TEM images of mono-layer graphene akes. (c) Electron diffraction pattern of the white spot region in (b).

Inset: Diffraction intensities taken along the 12 10 to 2 110 axis. (d) AFM image (1 m
1 m) showing the thickness of a mono-layer
graphene ake on a mica substrate.

Fig. 2(a), the spectra are featureless in the visible-IR
region, and there is a strong absorption band at around 270
nm, indicating that the graphene in the ethanol/water
solution does not have any disruption in electronic
structure. In comparison, the reported peak absorbance of
GO from chemical oxidation methods usually has a blue
shift to about 231 nm [23,28,3336]. After GO is reduced
to rGO, the peak absorbance would gradually red shift to
near 270 nm.
The role of ethanol addition is remarkable. Deionized
water itself is not soluble to graphene (Fig. 2(b)). But, by
addition of ethanol, the absorption intensity signicantly
increased and reached a maximum point at ~70 vol.%
ethanol, corresponding to a graphene concentration of
0.05 mg/mL. Further increasing the ethanol content led to
the decrease in graphene concentration. In the mono-
solvent of ethanol, there was almost no graphene.
To clarify the role of the solvent in the exfoliation
process, immediately after the sonication of graphite akes
in mono-water were nished, ethanol was added to make
the solution a mixture containing 70 vol.% ethanol in
water; then the dispersion was centrifugated and decanted.
It was observed that there was no noticeable graphene
detected in the nal dispersion by the absorbance
measurement. Similarly, for the case when water and
ethanol were exchanged to repeat the above procedure,
there was also no noticeable graphene detected in the nal
dispersion. Therefore, it may be concluded that graphene
can hardly be exfoliated from graphite in either water or
ethanol alone, at least, under the present experimental
conditions.
The origin of dispersibility improvement needs some
discussion. To predict if one substance can dissolve in
another, Hansen solubility parameters (HSPs) were intro-
duced and had been widely used for selecting solvents for
polymers [37]. In terms of the basic theory, the solubility
parameter can be divided into dispersive (d), polar (p)
and hydrogen-bonding (h) components [3839]:
 Wei-Wei LIU et al. Exfoliation and dispersion of graphene in ethanol-water mixtures
Fig. 2 (a) UV-vis absorbance results of the solutions with
different ethanol concentrations. (b) Dependence of Ra and
graphene concentration on the volume fraction of ethanol, with an
absorbance coefcient of 3182 L$g1$m1 at 660 nm. Inset:
Photographs of the solutions with different ethanol concentrations
in water.
2 2d 2p 2h (1)
Based on the idea of like dissolves like, substances
with the same HSP{d, p, h} will be likely to be mixable.
To characterize the dispersibility of graphene in the mixed
solution, the solubility parameter distance Ra is used here
[39]:
Ra 4dG dM 2 pG pM 2 hG hM 2 1=2
where the subscripts G and M denote graphene and mixed
solvent, respectively.
For calculation of Ra, it is necessary to nd the HSP
values for the mixture. In the case of the mixed solvent
containing water and ethanol, a relationship between the
HSP value of the mixture and its individual components
can be dened [40]. That is, the HSP value of the mixture is
equal to the sum of the products of the respective volume
fractions of the components and their corresponding HSP
values [41]:
179
dM e de 1 e dw (3)
pM e pe 1 e pw (4)
hM e he 1 e hw (5)
where the subscripts e and w, respectively, represent
ethanol and water, and fe is the volume fraction of ethanol.
From Eqs. (2)(5), a relation between Ra and fe can be
established as:
Ra f4dG e de 1 e dw 2
pG e pe 1 e pw 2
1=2
hG e he 1 e hw 2 g (6)
Taking the HSP value {15.8, 8.8, 19.4} for ethanol, and
the average value of {18.1, 17.1, 16.9} and {15.1, 20.4,
16.5} for water [37], and {18.0, 9.3, 7.7} for graphene [42],
the solubility parameter distance Ra is plotted as a
function of the ethanol volume fraction e in Fig. 2(b). The
plot shows a substantial decrease in Ra with ethanol
addition, mainly related to the decrease in the polar
bonding of the water component of the solubility parameter
in the mixture (Fig. 3). After having reached a minimum
value at ~60% ethanol, Ra slightly increases with the
further addition of ethanol. This may be due to a further
decrease in the hydrogen-bonding component of the
solubility parameter (Fig. 3). Such variation of Ra agrees
well with the observed change of graphene concentration
when the ethanol volume fraction e in the mixture
increases, as shown in Fig. 2(b). Therefore, it is suggested
that by mixing ethanol with water at a proper proportion,
the HSP of the mixed solution trends to match that for
graphene and thus is more dispersible to graphene.
From the graphene water/ethanol dispersion, it is easy to
form a thin lm by ltration [29]. Since the concentration
of graphene in the solution is known, the thickness of the
(2)
thin lm can be varied by controlling the volume of the
solution used for ltration. After having been transferred
from the membrane to a glass substrate, the thickness of the
lm was determined by AFM measurements. Even with a
large thickness of 50 nm (Fig. 4(a)), the lm possessed high
optical transmittance from 300 to 1100 nm (Fig. 4(b)),
revealing a wide transmittance window that is well suited
for infrared applications.
To improve the electrical conductivity, the lms were
annealed at 300C in different environments (air, nitrogen,
or vacuum) for 2 h. It was found that, whatever the
180 Front. Mater. Sci. 2012, 6(2): 176182
Fig. 3 The HSP components of dispersive (d), polar (p) and
hydrogen-bonding (h) for the ethanol/water mixtures plotted as a
function of the volume fraction of ethanol (e).
Fig. 4 (a) Image of a graphene lm on a glass substrate put on a
university logo. (b) Optical transmittance of the lm on a glass
substrate.
environment was, all the sheet resistance of graphene lms
decreased by about 20 times after annealing (Table 1). This
is probably because the lms are sensitive to the change in
Table 1 Sheet resistivity of graphene lms before and after annealing
(300C, 2 h) in different environments
Sheet resistivity /(k$sq1)
Graphene
As prepared After annealing
lm
before annealing N2 Air Vacuum
No. 1 156 12.3 7.1 9
No. 2 118.3 6.1 5.4 5.3
No. 3 209.8 8 7.6 6.8
ake network connectivity; thermal treatment might have
enabled the graphene sheets closer to the percolation
threshold, thus improved the ake-ake contacts and
reduced the resistance between two akes.
In this communication, we demonstrated a method for
exfoliation and dispersion of graphene in ethanol/water
mixtures. The prepared graphene is of few layers and
mono-layer with well maintained graphitic structure. The
composition of the ethanol/water mixture was found to be
crucial for both exfoliation and dispersion, and the
maximum concentration of graphene was observed in the
aqueous solution containing 70 vol.% ethanol. Further-
more, the obtained graphene dispersion was stable for years
without the usage of any surfactants, which can be easy to
prepare transparent and conductive graphene lms by
vacuum ltering or spray method, and does not need
special post-treatment to remove the impurity, which could
be benecial for potential applications in electronic, optic
and energy areas.
Acknowledgements JNW is thankful to the research fund (Project #
50871067) from the National Natural Science Foundation of China and the
National 863 Funds (2007AA05Z128 and 2009AA034400) from the
Ministry of Science and Technology of China.
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