Materials Letters 63 (2009) 1987–1989

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Production of few-layer graphene by supercritical CO2 exfoliation of graphite

Nen-Wen Pu a, Chung-An Wang b, Yu Sung c, Yih-Ming Liu a, Ming-Der Ger a,⁎
a
Department of Applied Chemistry and Materials Science, Chung Cheng Institute of Technology, National Defense University, Taiwan 335, ROC
b
Graduate School of Defense Science, Chung Cheng Institute of Technology, National Defense University, Taiwan 335, ROC
c
Chemical System Research Division, Chung Shan Institute of Science and Technology, Taiwan 335, ROC

a r t i c l e i n f o a b s t r a c t

Article history: In this study, the authors report a supercritical CO2 processing technique for intercalating and exfoliating
Received 3 November 2008 layered graphite. Few-layer graphene is produced by immersing powdered natural graphite in supercritical CO2
Accepted 14 June 2009 for 30 min followed by rapidly depressurizing the supercritical fluid to expand and exfoliate graphite. The
Available online 22 June 2009
graphene nanosheets are collected by discharging the expanding CO2 gas directly into a solution containing
dispersant sodium dodecyl sulfate (SDS) to avoid restacking. Atomic force microscopy (AFM) shows that the
Keywords:
Graphene
typical graphene sheet contains about 10 atomic layers. This technique offers a low-cost, simple approach to
Supercritical carbon dioxide large-scale production of pure graphene sheets without the need for complicated processing steps or chemical
Exfoliation treatment.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction
In recent years, graphene—a new allotrope of carbon in two-
dimensional (2D) form—was discovered and immediately attracted
great attention from both the experimental and theoretical scientists
[1–3]. Single-layer graphene is a planar sp2-bonded six-membered-
ring sheet of carbon, and is the basic building block for CNTs,
buckyballs, and graphite [3]. Single-layer graphene is supposed to be
a gapless semiconductor with a linear dispersion relation [4]. The
electronic band structure rapidly evolves with the number of layers [5],
so single-, double-, and few-layer graphene can be distinguished as
three different types of 2D crystals [3]. Therefore few-layer graphene is
a bridge between pure 2D and bulk systems, and can be used to study
the interesting physics at the crossover regime [6].
This new material is expected to have plenty of unique properties
such as high thermal conductivity, mechanical stiffness, and fracture
strength [7], and the exceptional electrical mobility due to the
extraordinary carrier transport behavior [3]. Although the realization of
most graphene-based devices still requires great research effort, the
application of graphene as a filler material for polymer nanocomposites
can be easily implemented. However, efficient approaches to produce
pure and well-separated graphene sheets in large quantities are required.
Mechanical cleavage of graphite is an easy way to obtain pure
graphene sheets and is widely used by many researchers [1]. Unfortu-
nately the productivity is too low for any large-scale use. Chemical
oxidation of graphite followed by subsequent exfoliation is more suitable
for bulk-quantity production of graphene sheets [8]. However, the
chemical modification of graphene might be undesirable for many
⁎ Corresponding author. Tel.: +886 3 389 1716; fax: +886 3 389 2494.
E-mail address: mdger@ccit.edu.tw (M.-D. Ger).
applications. For example, the exfoliated graphene oxide (GO) sheets are
electrically insulating unless converted back to graphene by chemical
reduction. These chemical conversion steps make the manufacturing
process more complicated, time-consuming, and costly. In addition, it is
difficult to obtain pure graphene due to the bonded functional groups
such as hydroxyl, carboxyl, and epoxy [8,9], and the residual chemicals in
the solution.
Supercritical fluids have been utilized to intercalate and delaminate
tightly-stacked layered materials such as clay and graphite [10–13].
When a substance is maintained above its critical temperature (TC) and
critical pressure (PC), it exists in a supercritical fluid phase having both
gaseous and liquid properties. It can penetrate many materials like gas
due to the low viscosity, zero surface tension, and high diffusivity, and
dissolve materials like liquid. Supercritical CO2 is widely used as a
nonflammable, nontoxic, environmentally friendly solvent with an easily
accessible critical point (TC = 31.1 °C and PC = 73.8 b). Recently, Gulari
and Serhatkulu used supercritical CO2 as a processing medium to diffuse
a coating agent (polydimethylsiloxane, PDMS) between layered graphite
particles [13]. Delaminated graphite particles coated with the coating
agent were obtained by catastrophic depressurization of the supercritical
CO2. The coating agent prevents the reformation of covalent bonds
between the delaminated graphite particles, so these particles may be
uniformly dispersed in a polymer to form a graphite–polymer
nanocomposite. However, in many applications the presence of foreign
molecules or polymers is undesirable, and a way to produce relatively
clean graphene sheets while keeping them well separated is needed.
In this work, the authors demonstrate a technique for producing few-
layer graphene by supercritical CO2 exfoliation of natural graphite. One
major advantage of supercritical CO2 over other solvents is the ease to
obtain high purity graphene by simply depressurizing, which allows the
supercritical CO2 to return to gas phase and evaporate, leaving no solvent

0167-577X/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2009.06.031
1988 N.-W. Pu et al. / Materials Letters 63 (2009) 1987–1989
Fig. 1. Schematic diagram of the supercritical CO2 processing system.
residues. To avoid aggregation through van der Waals interaction, these
exfoliated graphene nanosheets are dispersed in a solution of sodium
dodecyl sulfate (SDS). The simplicity, high productivity, low cost, and
short processing time make this technique suitable for large-scale
manufacturing.
2. Experimental
Commercial powdered natural graphite (from Alfa Aesar) was used
as our starting material. The commercial graphite has a particle size of
~70 μm with a purity of 99.99995% and a density of 2.25 g/cm3. Fig. 1
shows the schematic diagram of our fabrication apparatus. One gram of
graphite was placed in a high-pressure vessel with a heater and a
temperature controller. CO2 was then added into the vessel until the
pressure reached 100 b. Heat was applied to the vessel so that the
temperature of the vessel was kept at 45 °C. The graphite was immersed
in the supercritical fluid for 30 min.
Transmission electron microscopy (TEM) and atomic force micro-
scopy (AFM) were used to characterize the exfoliated graphene sheets.
The morphology of the graphene was examined with TEM (JEOL, JEM-
2000EXII, operating at 100 kV) and the result was compared to that of
untreated graphite. The roughness and film thickness of the sheets were
observed by tapping-mode AFM (Digital Instruments, MultiMode SPM/
NanoScope IIIa, tip material: n+-silicon; tip height: 10–15 µm; force
constant: 10–130 N/m). For AFM observation, a few drops of the
solution containing dispersed graphene were put on a Si substrate and
Fig. 2. (a) Top-view and (b) cross-section FE-SEM images of untreated graphite particles. (c) Top-view TEM image of a small flake of the graphite particle.
Fig. 3. TEM image of exfoliated few-layer graphene.
dried by baking. For TEM observation, the solution was directly dropped
on the carbon film coated copper grids.
3. Results and discussion
During the 30-min immersion in the supercritical fluid, the super-
critical CO2 diffused in between the layers of graphite due to its low
viscosity, high diffusivity, and small molecule size. The CO2-intercalated
graphite was forced to exfoliate or delaminate by the expansion of the
supercritical CO2 disposed interstitially between the layers upon rapid
depressurization of the vessel. The depressurization was performed by
opening a blow-off valve and the gas was released at a rate of about
40 mL/s. Compared to the conventional chemical oxidation and
exfoliation approach, where the exfoliation is caused by thermal
expansion of the gases trapped between the graphene sheets, our
method offers a much faster expansion mechanism, and thus a stronger
force to push the adjacent layers apart. In addition, our method offers a
way to avoid undesirable acid solvents and high temperature heating
processes. The graphene nanosheets were collected by discharging the
expanding CO2 gas directly into an aqueous solution within a container.
The solution contained 20 ppm SDS—a dispersant to avoid restacking of
the separated graphene sheets, and the graphene was well dispersed in
the solution.
The authors first examined the untreated graphite particles with a
field emission scanning electron microscope (FE-SEM; JEOL, JSM-6500F,
operating at 15 kV). Fig. 2(a) shows the top-view FE-SEM image of a
natural graphite particle. The particle size of natural graphite is around
20–40 µm. Fig. 2(b) shows the FE-SEM image of the cross-section of
nature graphite. The thickness is around 0.9–1.5 µm, and it clearly shows
a layered structure. Fig. 2(c) shows the TEM image of a small flake of the
graphite particle. The opacity of the graphite indicates that the electron
beam hardly penetrates through the thick structure.
The TEM image of an exfoliated sheet is shown in Fig. 3. The lateral
extent of a typical graphene sheet is a few micrometers. Compared to the
 N.-W. Pu et al. / Materials Letters 63 (2009) 1987–1989
Fig. 4. AFM scan of few-layer graphene: (a) pseudo-3D representation of a 1.5 µm × 1.5 µm scan of an individual graphene sheet. (b) 3 µm × 3 µm AFM topography image. (c) Cross-
section through the sheet shown in (b) (position indicated by the black line) exhibiting a height of 3.8 nm.
TEM image of untreated graphite (Fig. 1(c)), which is too thick for the
electron beam to penetrate, the exfoliated graphene sheet is rather
transparent, indicating a significantly reduced thickness. The TEM
micrograph also shows that there are several sections with different
numbers of atomic layers.
AFM is used to quantitatively analyze the thickness of the graphene
sheets, and the results are shown in Fig. 4. Fig. 4(a) displays the
pseudo-3D representation of a 1.5 µm × 1.5 µm scan of an individual
graphene sheet. Fig. 4(b) shows a 3 µm × 3 µm AFM topography image.
It reveals that the exfoliated sheets are well dispersed in the SDS
solution. Regions of different step heights are observed. A cross-
section through a typical graphene sheet (along the black line shown
in (b)) is depicted in Fig. 4(c). The minimum step height of the sheet
is 3.8 nm, which most probably corresponds to the thickness of a 10-
layer graphene. Based on the estimates by SEM, TEM, and particle size
analysis, the weight ratio of the exfoliated graphite after reaction was
approximately 30 to 40%.
4. Conclusions
The authors demonstrate a supercritical fluid processing technique
for producing few-layer graphene. After a treatment with supercritical
CO2 at 100 b and 45 °C for 30 min, powdered natural graphite is exfo-
liated by the instantaneous expansion of CO2 during an abrupt
depressurization step. The exfoliated graphene is dispersed in a solution
of SDS. The morphology of the few-layer graphene nanosheets is
examined with TEM and AFM. The results show that the graphene sheets
are well separated and the typical thickness is about 10 atomic layers.
There are several advantages in this technique. First of all, similar to
chemical conversion approaches, this technique is suitable for large-
quantity production of graphene. But the purity of the produced
1989
graphene is much better because this technique does not involve any
steps that convert graphene into graphite oxide or introduce any
functional groups, impurities, or coating agents. The yield of pure
graphene sheets in this technique is as high as ~30 to 40 wt.%. In addition,
the process is very simple and fast, and the costs for equipment and
manufacturing are very low. The authors believe that it can find
applications to the production of graphene-based nanocomposite
materials.
Acknowledgement
This project is sponsored by the National Science Council of Taiwan
under grant no. NSC 97-2221-E-606-001.
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