Carbon 45 (2007) 1578–1582

www.elsevier.com/locate/carbon

Electrical conductivity of graphite/polystyrene composites made

from potassium intercalated graphite
a,c
Hyuncheol Kim , H. Thomas Hahn a, Lisa M. Viculis b, Scott Gilje b, Richard B. Kaner b,*

a
Mechanical and Aerospace Department, University of California, Los Angeles, CA 90095, USA
b
Chemistry and Biochemistry Department and California Nanosystems Institute, University of California, Los Angeles, CA 90095, USA
c
Research Park, LG Chemical Ltd., Daejeon 305-380, Republic of Korea

Received 29 August 2005; accepted 13 February 2007

Available online 12 March 2007

Abstract

Composites between graphite and polystyrene have been synthesized starting from potassium intercalated graphite and styrene vapor.
This in situ polymerization process can be used to make electrically conductive composites containing well-dispersed thin graphite sheets.
The conductivities of the composites increase as the number of ordered carbon layers increases. With only 10% graphite in a polystyrene
matrix, an electrical conductivity up to 1.3 · 10 1 S/cm can be obtained. The key is synthesizing a material with at least four ordered
graphite layers (a stage IV complex) separated by polystyrene. This composite shows an improvement in conductivity over a control
composite made by radical polymerization of styrene containing the same amount of dispersed graphite which had a conductivity of
5.0 · 10 3 S/cm. Characterization of the complexes by powder X-ray diffraction, scanning electron microscopy and electrical conductiv-
ity is presented.
 2007 Elsevier Ltd. All rights reserved.

1. Introduction galleries, in situ polymerization has been carried out with

Thin graphite sheets offer excellent potential as rein-
forcement material for composites because of their high
stiffness and strength coupled with high aspect ratio (planar
dimension vs. thickness) and low weight. The high rein-
forcement efficiency of fully exfoliated silicate clays is
well-known [1–3]. Therefore, for realizing the reinforce-
ment potential of graphite sheets, it is important to exam-
ine how different numbers of stacked sheets interleaved
with polymer layers affect the physical properties of the
resulting composite.
An ideal graphite/polymer composite would consist of
individual graphite sheets separated by polymer in order
to fully disperse the graphite thereby maximizing any prop-
erty enhancement. In attempts to create a composite com-
prised of graphite layers with polymer filling the interlayer
*
Corresponding author. Fax: +1 310 206 4038.
E-mail address: kaner@chem.ucla.edu (R.B. Kaner).
liquid styrene monomer and potassium–graphite intercala-
tion compounds. However, good intercalation of polysty-
rene between graphite sheets has not been achieved by
this method so far [4–7], likely because potassium interca-
lated graphites are very reactive toward styrene monomer
and therefore most styrene molecules polymerize at the
potassium intercalated graphite surface before they can
penetrate into the interlayer galleries. As a result, the inte-
rior remains essentially unchanged because styrene is
excluded. On the other hand, Shioyama [8–12] found that
in situ polymerization using stage I or II alkali metal–
graphite intercalation compounds with a vaporized mono-
mer such as styrene or isoprene at 0.25 wt% of graphite can
produce polymer within the graphite galleries. Stage refers
to the number of graphite host layers divided by the num-
ber of guest layers that occur periodically in the galleries.
For example, if every carbon layer in graphite is interca-
lated, a stage I compound forms, while intercalating on
average every other layer results in a stage II compound.
Here our objective is to examine how the intercalation

0008-6223/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2007.02.035
 H. Kim et al. / Carbon 45 (2007) 1578–1582 1579

stage affects the structure and electrical conductivity of the

resulting composite, since this property is often sensitive to
the thickness of the unintercalated graphite layers [13,14].
Synthesizing higher stage intercalation compounds will be
shown to be critical in achieving high conductivities.

2. Experimental Fig. 1. Schematic domain model showing graphite host layers intercalated
with different numbers of potassium guest layers.
2.1. Composite preparation

Graphite/polystyrene nanocomposites were prepared by in situ poly-

merization from distilled styrene and different stage potassium intercalated
graphites. For preparation of the potassium intercalation compounds [14–
20], a mixture of graphite and potassium were placed in a sealed, evacu-
ated Pyrex tube in a helium filled drybox. The tube was evacuated, sealed
and then heated at 220 C for 3 days. The host graphite used was
expanded natural graphite (3775, Asbury Graphite Mills, Inc.). The
3775 graphite was chosen to facilitate exfoliation after intercalation since
it has been pre-exfoliated by rapid heating in a 600 C furnace after acid
intercalation. This process along with an average plate diameter of 6 lm
as determined by SEM, yields a graphite with an a,b:c plane aspect ratio
greater than 100:1. The pre-treatment and exfoliation undergone by the
3775 graphite facilitates the dispersion and fabrication of a composite.
The pre-treatment also allows a good dispersion to be achieved more eas-
ily, with shorter mixing and sonication times than starting from unexfoli-
ated graphite.
The molar ratio of potassium to carbon in the reaction mixture was
varied in order to obtain different intercalation stages of potassium inter-
calated graphites [20–24]. Table 1 indicates the different weight ratios used
to form stage I KC8, stage II KC24, stage III KC36, and stage IV KC48.
The idealized structures expected for the different intercalation stages
are shown in Fig. 1 [25].
The potassium intercalation complexes were then allowed to react with
distilled styrene (Aldrich) at room temperature by first evacuating the
Pyrex tube containing the potassium–graphite and then exposing it to sat-
urated vapors of styrene by placing liquid styrene in a separate tube con-
nected on the same glass vacuum line and opening a stop-cock in between
them. Styrene evaporated, penetrated into the interlayer galleries of the
potassium intercalated graphites and then underwent anionic polymeriza-
tion in the galleries [9]. The potassium intercalated graphites slowly
expanded due to styrene polymerization in the graphite galleries until
the source of styrene was exhausted. The reaction took a minimum of
24–48 h for the styrene to be consumed. In the end, graphite/polystyrene
composites were obtained in powder form. This powder was annealed at
120 C for one hour to ensure complete polymerization. The amount of
styrene polymerized was adjusted so that the graphite content was kept
at 10 wt% in each of the composites. Fig. 2 shows a cartoon of the
in situ polymerization of styrene in the potassium intercalated graphite
galleries. For comparison to all the composites made from the intercala-
tion compounds, a control composite of 3775 graphite with polystyrene
was prepared through radical polymerization without the intercalation
step. The 3775 graphite was added into distilled styrene, and the mixture
was stirred with a high shear mixer at 20,000 rpm for 15 min, and then
sonicated at 120 W for 5 min. Trigonox 239 A (Akzo Nobel) as an initia-
tor and 6% cobalt naphthenate (Dow Chemical Company) as a promoter
for the polymerization were added into the mixture of styrene and 3775
Table 1
Weight ratios for different stage potassium intercalated graphites
Stage Graphite (g) Potassium (g) Compound Color
I 1 0.407 KC8 Gold
II 3 0.407 KC24 Blue
III 4.5 0.407 KC36 Blue
IV 6 0.407 KC48 Blue
Fig. 2. A schematic illustration of what happens when stage I potassium
intercalated graphite (KC8) is exposed to styrene vapor.
graphite. The polymerization proceeded at room temperature and then
post-curing was carried out at 120 C for 2 h. The amount of graphite
in this composite was also kept at 10 wt%.
2.2. Characterization
The reaction products were analyzed with powder X-ray diffraction
(XRD) and scanning electron microscopy (SEM). X-ray diffraction scans
of the composites were obtained using a Crystal Logic diffractometer with
Ni-filtered Cu Ka (k = 1.5405) radiation. Powder X-ray diffraction pat-
terns were taken in 0.05 steps at 3 s per step. The samples were attached
to glass slides using double sided tape. For electron microscopy, samples
were attached to metal disks with carbon tape, and imaged with a JEOL
SM-71010 field emission SEM.
Volume conductivities of the composites were measured in a two-point
probe test. The powders of composites from potassium intercalated graph-
ites were pressed at room temperature under about 3.4 MPa of pressure to
make a disk with a diameter of 13 mm and an approximate thickness of
5 mm. The pressing allowed for sufficient mechanical contact between
graphite grains to give reasonably accurate and reproducible conductivi-
ties. Silver paste was painted on to the disk surface to form an electrode
and the distance between the electrical contacts was 5 mm. The sample
dimension of the composite from radical polymerization was
10 · 10 · 3 mm. Silver paste was painted on to the specimen surface to
form an electrode, and the distance between the electrical contacts was
3 mm. Ohmic resistance was measured with a multimeter (Radio Shack)
and converted into volume conductivity based on the specimen dimen-
sions. Five specimens were used for each test.
3. Results and discussion
3.1. X-ray powder diffraction of graphite/polystyrene
composites
Fig. 3a shows a powder X-ray diffraction pattern of the
control polymer composite made from 3775 graphite com-
posite with polystyrene formed by radical polymerization.
A strong crystalline graphite peak at 26.5 2h and two
broad polystyrene peaks centered around 10 and 20 2h
are observed in the X-ray powder diffraction pattern.
1580 H. Kim et al. / Carbon 45 (2007) 1578–1582
Fig. 3. Powder X-ray diffraction patterns of the following composites: (a)
graphite/polystyrene, (b) stage I KC8/polystyrene, (c) stage II KC24/
polystyrene, (d) stage III KC36/polystyrene and (e) stage IV KC48/
polystyrene.
A peak broadening analysis of the crystalline graphite peak
at 26.5 2h, was carried out using the Sherrer equation. The
peak broadening analysis indicates that no broadening has
occurred relative to a ground silicon standard and there-
fore after styrene polymerization the graphite crystallites
in the control graphite/polystyrene composite remain lar-
ger than 200 nm. Powder X-ray diffraction patterns of
graphite/polystyrene composites synthesized by exposing
stage I, II, III and IV graphite intercalation compounds
to styrene vapor are shown in Fig. 3b–e, respectively.
Fig. 3b indicates that a composite made from first stage
KC8 with polystyrene shows very little of the usually most
intense 0 0 2 peak for crystalline graphite at 26.5 2h. This
suggests that the graphite/polystyrene composite has no
long-range order for graphite sheets as a result of the poly-
merization of styrene between essentially every layer of
graphite. Looking down the diffraction patterns from
Fig. 3b–e clearly shows that the 0 0 2 peak intensity for
crystalline graphite at 26.5 2h increases as the intercalation
stage increases. Although some pristine, unintercalated
graphite could be present, the increasing number of intact
ordered graphite layers present in higher stage complexes
can readily account for this. The idea is that carrying out
chemical reactions in the galleries between graphite layers
will have little affect on the ordering between uninterca-
lated graphite sheets. Therefore, the greater the number
of unintercalated layers, the more intense the X-ray diffrac-
tion peak for crystalline graphite is expected to be. It is thus
not surprising that among the intercalation compounds,
the strongest graphite diffraction peak at 26.5 2h occurs
for the stage IV compound (KC48), followed by the stage
III (KC36), II (KC24), and I (KC8), respectively. Note that
higher temperature intercalation reactions are sometimes
used to achieve more highly ordered stage III and stage
IV potassium–graphite intercalation compounds [26,27].
However, while the methods described here may produce
some mixed stages with nominal values centered about
stage III for KC36 and Stage IV for KC48, they enable a
straightforward method for creating well-dispersed com-
posites [24].
3.2. Scanning electron micrographs of graphite/polystyrene
composites
Scanning electron micrographs (SEMs) are presented in
Fig. 4 for (a), the 3775 graphite (3775, Asbury Graphite
Mills, Inc) control sample, (b), a composite made by react-
ing styrene with stage I potassium intercalated graphite
(KC8) and (c), a composite made by reacting styrene with
stage IV potassium intercalated graphite (KC48). While,
the 3775 graphite shows a plate-like morphology, a com-
posite made by reacting stage I KC8 with styrene does
not. On the other hand, a composite made by reacting
stage IV KC48 with styrene does show some platelet-like
structures. This indicates that only the potassium interca-
lated galleries are open to styrene polymerization and the
bound graphitic layers remain intact after styrene
polymerization.
3.3. Electrical conductivity of graphite/polystyrene
composites
The electrical volume conductivities of the composites
(Fig. 5) were measured using a two-point probe technique
and reveal an interesting phenomenon. The composite
made from stage I KC8 and styrene shows a conductivity
of less than 10 9 S/cm. This means that when graphite is
fully intercalated with polystyrene, the material is a rather
poor electrical conductor. The stage II KC24/styrene com-
posite also displays a relatively low conductivity of less
than 10 5 S/cm. As the number of attached graphite sheets
increases, the volume conductivity increases, reaching
10 4 S/cm for a composite comprised of stage III KC36
with styrene and 1.3 · 10 1 S/cm for a composite com-
prised of stage IV KC48 with styrene. Note that the volume
conductivity of the stage IV KC48/styrene composite is
higher than that of the control composite made by radical
polymerization of styrene containing the same amount of
dispersed 3775 graphite. It appears that the number of
bound graphite layers remaining intact strongly affects
the electrical conductivity of composites with polystyrene.
This is consistent with the fact that single graphite layers
are zero band gap semiconductors while graphite crystal-
lites are semimetals [13]. However, as we go to higher stage
number it may be possible that the volume fraction of poly-
styrene to graphite within the graphite galleries may change
between composites of different stage number. The change
 H. Kim et al. / Carbon 45 (2007) 1578–1582
Fig. 4. Scanning electron micrographs: (a) graphite, (b) a stage I KC8/
polystyrene composite and (c) a stage IV KC48/polystyrene composite.
in polystyrene volume fraction could create variations in
conductivity. Another possible reason for the change in
conductivity with respect to stage number is the presence
of defects as a result of intercalation. Since intercalation
induces defects in the graphite structure, conductivity is
expected to decrease with decreasing stage number since
defects are detrimental to conductivity. Along with the
increased defects brought about by lower stage intercala-
tion, the larger unintercalated crystalline regions of the
1581
Fig. 5. Electrical conductivities of graphite/polystyrene (PS) composites
made from stage I (KC8), stage II (KC24), stage III (KC36) and stage IV
(KC48) potassium intercalation compounds. A composite made from
radical polymerization of 3775 graphite and styrene is given for
comparison.
higher stage intercalation compounds should therefore pro-
vide better conductivity than the highly intercalated, lower
stage compounds where the crystalline regions are smaller.
The increase of conductivity with increasing crystallite size
helps to explain why the conductivity of the 3775 graphite/
polystyrene control composite, with no polystyrene inter-
laced between the galleries, is close to that of the stage
IV, KC48 composite.
4. Conclusions
We have successfully synthesized graphite/polystyrene
composites from potassium–graphite intercalation com-
pounds with stoichiometries of KC8, KC24, KC36 and
KC48 corresponding to stage I, II, III and IV K-GIC com-
pounds, respectively. The powder X-ray diffraction of these
compounds indicates that upon going from stage I to stage
IV K-GIC, an increase in the crystallinity is observed.
Scanning electron microscopy images are consistent show-
ing that a well-layered starting graphite becomes highly dis-
ordered after stage I intercalation followed by styrene
polymerization. An increase in in-plane ordering is
observed with higher stage graphites. Conductivity tests
demonstrate that the conductivity increases with increasing
stage. The volume conductivity of the stage IV KC48/poly-
styrene composite reaches 1.3 · 10 1 S/cm which is eight
orders of magnitude higher than the stage I KC8/polysty-
rene composite with a conductivity of 10 9 S/cm. The
KC48/polystyrene composite also showed a higher con-
ductivity than a control composite made by radical poly-
merization of styrene containing the same amount of
dispersed graphite. This is consistent with more intact lay-
ers of graphite creating improved pathways for conduction.
Thus, for applications requiring a high electrical conductiv-
ity, graphite intercalation compounds of stage IV or possi-
bly higher should be considered.
1582 H. Kim et al. / Carbon 45 (2007) 1578–1582
Acknowledgements
The authors thank the Air Force Office of Scientific
Research with B.L. Lee as the Program Manager and the
Raytheon Professorship in Manufacturing (HTH) for
financial support.
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