Numerous single-layer graphene sheets prepared from natural graphite by

non-chemical liquid-phase exfoliation

Ping-Cheng Hsu, Ting-An Lin, I-Shou Tsai
Department of Fiber and Composites Material, Feng Chia University, No. 100, Wenhwa Road, Seatwen, 40724 Taichung,
Taiwan
E-mail: istsai@fcu.edu.tw
Published in Micro & Nano Letters; Received on 8th July 2014; Accepted on 1st September 2014

A simple method was used to produce a high concentration of single-layer graphene sheets in a single organic solvent system, without using
any surfactants. In this experiment, the concentration of single-layer graphene sheets dispersed in solution increased as the sonication time
increased, but damage occurred after performing sonication for 120 min. The concentration of single-layer graphene sheets was 0.915 mg/
ml after sonication for 60 min. According to a transmission electron microscope image, the length of the single-layer graphene sheets was
23 m, and the width was 0.51 m. The perfect single-layer graphene sheets and the defective single-layer graphene sheets were
distinguished using selected-area electron diffraction. X-ray diffraction determined that the two-theta angle of the numerous single-layer
graphene sheets on a (002) plane was 25.57, but the one layer graphene sheets produced no peak along the (002) plane. According to
the Raman spectra, the ratio of ID/IG was 0.3, which indicated that the graphene sheets contained few defects.

1. Introduction: Recently, the novel carbon material graphene has

attracted much attention because it exhibits high thermal
conductivity, a high theoretical surface area, excellent transparent
properties and excellent mobility of charge carriers [18]. A
variety of methods are used for preparing graphene, such as the
micromechanical exfoliation of graphite [1], the chemical
reduction of graphene oxide [9], chemical vapour deposition [10]
and epitaxial growth [11, 12]. However, achieving high-quality
and high-yield stable production of single-layer and few-layer
graphene sheets remains a major challenge [1315]. Liquid-phase
exfoliation has been determined to be an effective method for the
mass production of single-layer graphene sheets [1619]. The
non-chemical liquid-phase exfoliation method has been used for
more than 50 years for chemically exfoliating graphite [17].
Hernandez et al. successfully produced graphene using natural
graphite powder dispersed in an organic solvent, such as
N-methyl-2-pyrrolidone
(NMP),
g-butyrolactone,
N,
N-dimethylacetamide and 1,3-dimethyl-2-imidazolidinone, and
the yield production of a single-layer graphene sheet was 18%
[17]. Puangbuppha et al. successfully dispersed graphene in
distilled water using sonication for three months after the
graphene was sonicated for 36 and 72 h [18]. Tasis et al. used a
mixture of 90% v/v 1,2-dichlorobenzene and 10% v/v isobutanol
exfoliated graphite, and reported that the dispersability reached
0.1 mg/ml and 90% enrichment in few-layer graphene, and the
layer number was less than ve [20]. This study determined a
method for obtaining high-concentration single-layer graphene
sheets dispersed in solution and stably dispersed in single organic
solvent without using any surfactants. Compared with other
methods, the proposed method has several advantages: it is low
cost, simple, effective and fast.
2. Experimental
2.1. Materials: For this work, the natural graphite powder (purity:
99%) was provided by Meso Tech. as raw material. NMP (purity:
99.3%) was used as a solvent, and was purchased from Echo
Chemicals Co. Ltd, Taiwan.
2.2. Exfoliation of single-layer graphene sheets: Natural graphite
was exfoliated into single-layer graphene sheets using the
nonchemical liquid-phase exfoliation method. In this work,

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sonication was used to exfoliate natural graphite in an organic

solvent. The Branson sonication instrument (Sonier 450D) used
in this work produces a frequency of 20 kHz and a total power of
400 W. As the liquid volume fraction was proportional to output
energy, the actual power used in this experiment was 240 W. The
single-layer graphene sheets dispersed in solution were prepared
in three steps. Firstly, 1 g of natural graphite and 50 ml of
organic solvent NMP were added to a beaker at room
temperature. Secondly, sonication was performed for 30, 60, 90
and 120 min. Finally, to obtain single-layer graphene sheets
dispersed in solution, the graphene-dispersed solution was
centrifuged at 2600 rpm for 20 min to collect the upper
graphene-dispersed solution because the theoretical density of the
single-layer graphene sheets was only 0.77 mg/m2 [2]. To
measure the weight of the single-layer graphene sheets, graphene
was turned into powder. The single-layer graphene powder was
made by upper single-layer graphene sheets dispersed in solution
and drying the sample at 400C for 1 h in an oven. The yield
production percentage of the single-layer graphene exfoliated
from 1 g of graphite was then calculated.
2.3. Characterisation: The maximum absorption wavelength of the
single-layer graphene sheets was analysed by conducting UVvis
spectroscopy, using a Chrom Tech (UV-1600). Transmission
electron microscopy (TEM) at an accelerating voltage of 150 kV
was used to obtain high-resolution TEM images (JEM-1200EX
II, Jeol Co., Japan). The morphology of the single-layer graphene
sheets was characterised using a scanning electron microscope
(SEM) (S3000-N, Hitachi, Japan). The crystallographic structure
of the single-layer graphene sheets was studied using a
multipurpose thin-lm X-ray diffractometer (D8 SSS, Bruker).
The Raman spectra were recorded using an excitation wavelength
of 532 nm (InVia Reex, Renishaw, UK) (2.41 eV), and the laser
power was maintained below 1 mW (PTT, BWll RAMarker).
3. Results and discussion
3.1. Yield of single-layer graphene sheets: To observe the colour of
single-layer graphene sheets dispersed in NMP, a picture was
captured using a digital camera, as shown in Fig. 1. Fig. 1 shows
the single-layer graphene sheets dispersed in solution under
different sonication times. The single-layer graphene sheets were

Micro & Nano Letters, 2014, Vol. 9, Iss. 12, pp. 922926
doi: 10.1049/mnl.2014.0415

Figure 1 Digital photograph of single-layer graphene sheets dispersed

solution under different sonication times
a 30 min
b 60 min
c 90 min
d 120 min

uniformly dispersed and sedimentation did not appear at the bottom

of the bottle over three to four months. The colour of the
single-layer graphene sheets dispersed in solution was black with
some dark brown, because the NMP was sensitive to the heat
produced by sonication. The black single-layer graphene sheets
dispersed in solution were collected from each sample, placed in
pure NMP solvent and diluted 10, 50, 100 and 200 times
individually for each sample to verify the excellent transparent
property of the single-layer graphene sheets, shown in Table 1.
The concentration of the single-layer graphene sheets was
extremely high, which enabled the stable dispersion of these
single-layer graphene sheets in a single organic solvent system,
using sonication and without using any surfactants. UVvis
spectroscopy was used to determine the maximum wavelength
absorption of the single-layer graphene sheets, as shown in Fig. 2.
Fig. 2 shows the maximum wavelength absorption of single-layer
graphene sheets after being subjected to various sonication times
and repeated dilutions. When the same sonication time was used,
a blue-shift phenomenon occurred as the number of dilutions
increased. Blue shift means that the maximum wavelength absorption shifted from a long wavelength to a short wavelength, which
was represented by the single-layer graphene sheets dispersed in solution becoming more transparent, as shown in Fig. 2. We observed
that after being diluted 200 times (<0.008 mg/ml) for each sample,
black single-layer graphene sheets dispersed in solution became
transparent. The yield production was calculated by drying the
single-layer graphene sheets dispersed in solution in an oven to
obtain the single-layer graphene powder, which was then weighed.
Fig. 3 shows the digital photograph of the single-layer graphene
powder undergoing various sonication times. The yield production
of the single-layer graphene powder varied according to the sonication time. The yield production of the single-layer graphene
Table 1 Concentration of single-layer graphene sheets dispersed solution
under different sonication times
Sonication time, min
30
60
90
120

Concentration, mg/ml
0.838
0.915
1.355
1.588

0.084
0.092
0.136
0.159

0.017
0.018
0.027
0.032

0.008
0.009
0.014
0.016

Micro & Nano Letters, 2014, Vol. 9, Iss. 12, pp. 922926
doi: 10.1049/mnl.2014.0415

0.004
0.005
0.007
0.008

Figure 2 UVvis absorption spectra of single-layer graphene sheets dispersed solution under different sonication times and different concentrations: raw solution (black line), dilute 10 (red line), 50 (blue line), 100
(pink line) and 200 times (green line)
a 30 min
b 60 min
c 90 min
d 120 min

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Figure 3 Digital photograph of single-layer graphene powder after 400C

in oven under different sonication times
a 30 min
b 60 min
c 90 min
d 120 min

Table 2 Yield of single-layer graphene powder after 400C in oven under

different sonication times
Sonication time, min
Powder, mg

30
41.91

60
45.77

90
67.74

120
79.42

powder sample (d) shown in Fig. 3 was signicantly higher than

that of the powder sample (b) shown in Fig. 3. Table 2 shows the
yield production of the single-layer graphene powder. The yield
production of single-layer graphene powder increased as the sonication time increased. The weight of the single-layer graphene
powder was calculated by exfoliating 1 g of natural graphite for
each sample.
3.2. TEM images of single-layer graphene sheets: Fig. 4 shows the
TEM image of numerous single-layer graphene sheets stacked next
to each other because of van der Waals forces. The length of the
single-layer graphene sheets was 23 m, and the width was
0.51 m. Fig. 5 shows the TEM and selected-area electron
diffraction (SAED) images of the single-layer graphene sheets
that underwent sonication for 60 and 120 min. The attened and
perfect surface of the TEM image of the stacked single-layer

Figure 4 TEM image of numerous single-layer graphene sheets in

0.915 mg/ml solid content

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Figure 5 TEM images and diffraction pattern

a Single-layer graphene sheets without defects after sonication 60 min
b Corresponding SADE diffraction pattern with (Fig. 5a)
c Defects in single-layer graphene sheets after sonication for 120 min
d Corresponding SADE diffraction pattern with (Fig. 5c)

graphene sheets is shown in Fig. 5a. Fig. 5b is the SAED image

of Fig. 5a, and a typical hexagonal crystalline structure can be
clearly observed [2]. Fig. 5c shows the TEM image of the
defective single-layer graphene sheets. The surfaces of the sheets
were most likely broken because the sonication time was too
long. Fig. 5d is the SAED image of Fig. 5c, and shows a typical
amorphous pattern, and the crystalline structure of the
single-layer graphene sheets was clearly damaged.
3.3. SEM micrographs of single-layer graphene powder: Fig. 6
shows the SEM micrographs of the single-layer graphene powder
after being dried at 400C for 1 h in an oven. Figs. 6a and b
show the single-layer graphene powder after being subjected to a

Figure 6 SEM micrographs of single-layer graphene powder after 400C in

oven
a 250 times, sonication time of 60 min
b 500 times, sonication time of 60 min
c 250 times, sonication time of 120 min
d 500 times, sonication time of 120 min

Micro & Nano Letters, 2014, Vol. 9, Iss. 12, pp. 922926
doi: 10.1049/mnl.2014.0415

angle, which were extremely similar to those of the natural

graphite XRD pattern.
3.5. Raman spectra of graphene sheets: Fig. 8 shows the samples
that underwent a sonication time of 60 and 120 min, and the
Raman spectra of the graphene sheets. The D-band at 1360
1365 cm1 represents the breathing mode of sp2 in rings [21].
The G-band at 1565 cm1 represents the in-plane bond-stretching
motion of the pairs of carbon sp2 atoms [22]. By observing the
shape and the intensity of the peak on the 2D-band, the number
of graphene sheet layers can be distinguished [23]. The Raman
spectra of the graphene sheets underwent sonication for 60 min,
the D-band was 1363 cm1, the G-band peak was 1565 cm1, the
2D-band peak was 2704 cm1 and the ID/IG ratio was 0.3, which
indicates few defects. In addition, the ID/IG ratio of the graphene
sheets that underwent a sonication time of 120 min was 0.62, and
the large amount of defects was correlated with the TEM results.
Figure 7 XRD pattern of single-layer graphene sheets impacted by sonication time

sonication time of 60 min; the length of the single-layer graphene

powder was 100 m, and the width was 200 m. Figs. 6c and d
show the single-layer graphene powder after undergoing a
sonication time of 120 min; the length of the single-layer
graphene powder was 100 m, and the width was 200 m. The
images were magnied 250 times, as shown in Figs. 6a and c,
and 500 times, as shown in Figs. 6b and d. The edge of the
single-layer graphene powder was smooth and the shape was that
of a slightly warped sheet because of the thermal temperature of
the oven, as shown in Figs. 6a and b. The size of the single-layer
graphene powder shown in Figs. 6c and d was smaller, shorter
and exhibited several cracks compared with those shown in
Figs. 6a and b, correlated with the TEM results.
3.4. XRD analysis of single-layer graphene sheets: Fig. 7 shows the
X-ray diffraction (XRD) pattern of the single-layer graphene sheets
that underwent various sonication times. The pattern that was
observed after sonication for both 30 and 60 min was a straight
line (need reference) because the single-layer graphene sheet did
not contain a second carbon atom layer and subsequently could
not be diffracted using X-ray radiation. A signicant peak on the
(002) plane and a 25.57 two-theta angle were observed after
sonication for both 90 and 120 min. Results derived from using a
longer sonication time to exfoliate numerous single-layer
graphene sheets showed that they were attracted to each other.
This revealed a strong peak on the (002) plane at a two-theta

4. Conclusion: In this experiment, a high concentration of

single-layer graphene sheets was successfully prepared using the
non-chemical liquid-phase exfoliation method. After undergoing
sonication for 60 min, the concentration of the perfect
single-layer graphene sheets dispersed in solution was 0.915 mg/
ml. According to the TEM and SAED images, the crystalline
structure of the single-layer graphene sheets was perfect, after a
sonication time of 60 min. The single-layer graphene sheets were
then dried in an oven and 45.77 mg of single-layer graphene
powder was obtained. The SEM analysis results were correlated
with the TEM results, revealing that a longer sonication time
causes defects in and damage to the single-layer graphene sheets.
The XRD results indicated that the two-theta value of the
single-layer graphene sheets depends on the sonication time.
When a longer sonication time was used to exfoliate numerous
single-layer graphene sheets, the single-layer graphene sheets
were attracted to each other because the two-theta value was
similar to that of natural graphite; in this experiment, the value
was 25.57. When the sonication time was 60 min, the Raman
spectra showed that the ID/IG ratio was 0.3, which indicates few
defects. Hence, based on the data obtained in this work using
numerous instruments, the optimal sonication time is 60 min. In
future studies, we will increase the concentration of single-layer
graphene sheets in a single organic solvent system and
water-based system.
5. Acknowledgments: The authors thank the National Science
Council of Taiwan for support (project numbers 101-2622E-035-010-CC3).
6 References

Figure 8 Raman spectra of graphene sheets impacted by sonication time

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doi: 10.1049/mnl.2014.0415

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Micro & Nano Letters, 2014, Vol. 9, Iss. 12, pp. 922926
doi: 10.1049/mnl.2014.0415