CARBON 5 0 ( 2 0 1 2 ) 3 0 6 4 –3 0 7 3

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The effect of graphite oxide on the thermoelectric properties

of polyaniline

Yuan Zhao a, Guang-Shi Tang a,*

, Zhong-Zhen Yu b, Jun-Shan Qi c

a
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
b
State Key Laboratory of Organic–Inorganic Composites, Department of Polymer Engineering, College of Materials Science and Engineering,
Beijing University of Chemical Technology, Beijing 100029, China
c
Institute of Plant Protection, Shandong Academy of Agricultural Sciences, Jinan 250100, China

A R T I C L E I N F O A B S T R A C T

Article history:
Received 29 November 2011
Accepted 1 March 2012
Available online 7 March 2012
Graphite oxide (GO)/ordered polyaniline (PANI) composites have been prepared through an
in situ polymerization. TEM, XRD, FTIR and XPS analyses show that the PANI grew along the
surface of exfoliated GO as a template to form a more ordered structure with high crystal-
linity during polymerization. Compared with pure PANI, both higher electrical conductivity
and higher Seebeck coefficient of GO/PANI composites result from the increased carrier
mobility, which is confirmed by Hall measurement. Strong interactions exist between
graphene oxide and PANI, including electrostatic forces, hydrogen bonding and p–p stack-
ing. There is no significant difference in thermal conductivity between GO/PANI compos-
ites and PANI. The maximum electrical conductivity and Seebeck coefficient of the
1
composites reach 751 S m and 28.31 lV K 1, respectively. The maximum thermoelectric
figure of merit is up to 4.86 · 10 4, 2 orders of magnitude higher than that of pure PANI.
 2012 Elsevier Ltd. All rights reserved.

1. Introduction
Since graphene, a one-atom layer of graphite, was isolated by
Novoselov et al. in 2004 [1], its excellent mechanical, thermal,
optical [2] and electronic properties [3,4] have attracted the
attention of scientists and enabled new kinds of electronic
devices [5–7] and sensors [8].
One route to make use of these properties for applications
is to incorporate graphene sheets into a matrix. Generally,
researchers start with graphite oxide (GO) to prepare graph-
ene/polymer composites. The exfoliated GO is a functional-
ized graphene, usually called graphene oxide, which is a
one-atom planar crystal with aromatic regions and aliphatic
regions. Aromatic regions have a similar structure to the
graphene’s p-bond structure. Aliphatic regions contain hydro-
xyl, carboxyl, carbonyl and epoxide groups, which is the ori-
gin of hydrophilicity of GO. GO has its natural advantages to
be an ideal filler for polymer resulted from that the GO still
possesses the most physical properties of graphene. The
functionalities on the surface of graphene can enhance the
dispersion of graphene in polymeric matrix and the interfa-
cial interaction between graphene and polymeric matrix. It
is well-known that the dispersion and interface interaction
are the key parameters in the evaluation of polymer-based
composites [9]. GO is separated into individual layers (graph-
ene oxide) after further treatment with ultrasonication, and
dispersed in a solvent in which a polymer or its monomer is
also dissolved. Chemical reduction may result in graphene
sheets within the polymer.
The synergistic effect of GO on the polymers has been
widely studied, such as enhanced mechanical properties
[10,11], electrical properties [12,13], thermal properties
[14,15] and flame retardancy [16,17]. However, to our knowl-
edge, the effect of GO on the thermoelectric properties of

* Corresponding author.
E-mail address: tgs1803@163.com (G.-S. Tang).
0008-6223/$ - see front matter  2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.carbon.2012.03.001
 CARBON 5 0 ( 20 1 2 ) 3 0 6 4–30 7 3
polymers has not been reported. The conversion between
heat and electrical energy can be achieved through thermo-
electric materials. There is no moving parts, no noise and
no waste in the conversion process, so thermoelectric materi-
als are believed to be a type of environment-friendly materi-
als. The dimensionless thermoelectric figure of merit
ZT = S2rT/k is usually used to evaluate the thermoelectric
properties. Obviously, a good thermoelectric material must
have excellent electrical conductivity r, high Seebeck coeffi-
cient S and low thermal conductivity k. The electrical conduc-
tivity r is given by the equation: r = qnl, where q is the charge
on the charge carrier, n is the carrier concentration, and l is
the charge carrier mobility.
Traditional thermoelectric materials include Bi–Te series,
Pb–Te series and Si–Ge series, in which Bi2Te3-based thermo-
electric materials have been proved to be the best bulk ther-
moelectric materials at room temperature. Nowadays, a new
type of thermoelectric materials with different microstruc-
ture from traditional materials, for example, nanowires or
superlattice nanowires, superlattice thin films, and nanocrys-
talline materials are in the ascendant [18]. Though a lot of re-
searches on inorganic thermoelectric materials have been
reported, the high cost and poor processing performance pre-
vent their applications. In contrast, polymers possess unique
features of low density, low cost due to rich resources, easy
synthesis, and easy processing into a light and flexible form.
Especially, polymers possess a low intrinsic thermal conduc-
tivity compared with inorganic materials. This provides a
motivation to investigate polymers as a new kind of applica-
ble thermoelectric materials [19,20]. Sun et al. tested the abil-
ity of the thermo-electric module composed of n–p organic
couples and pointed out that organic materials could be very
promising for future thermoelectric applications [21]. Some
studies show that conductive polymers including polyaniline
(PANI), polypyrrole and polythiophene exhibit attractive ther-
moelectric properties [22–26], with a record ZT reported for
poly(3,4-ethylenedioxythiophene) [27].
In this work, we optimized the power factor S2r of the con-
ductive polymer polyaniline by using GO as fillers. Meng et al.
[28] used carbon nanotubes (CNTs) as fillers and obtained a
CNT/PANI composite with a power factor of 2 · 10 5 W m 1
K 2, which is 2 orders of magnitude more than that of pure
PANI. Yao et al. [29] also used a CNT network as filler and found
that the Seebeck coefficient S and power factor P were several
times larger than those of either of the individual components.
That CNTs tend clump, combined with their rolled walls and
high cost, brings about a difficulty in preparing CNT/polymer
composites. In contrast, GO as a substitute for CNT is cheap
and requires no helicity control. The exfoliated GO possesses
large surface area and could form stronger interactions than
tubular CNTs with PANI. Compared with CNTs, the graphene
oxide may be expected to blend with a polymer more easily
to improve the thermoelectric properties of the polymer.
In polymerization, graphene oxide played a role of tem-
plate, the PANI grew orderly on the surface of graphene oxide
due to the p–p interaction, electrostatic forces and the hydro-
gen bonding existed between graphene oxide and PANI. The
increased charge carrier mobility results in both the increased
electrical conductivity r and increased Seebeck coefficient S.
To our knowledge, no attempt has been made to apply graph-
3065
ene oxide as a template to improve the thermoelectric proper-
ties of PANI.
2. Experimental
2.1. Materials
Natural graphite flakes with a mean size of 48 lm were sup-
plied by Huadong Graphite Factory.
Hydrochloric acid (HCl), nitric acid (HNO3), sulfuric acid
(H2SO4), potassium chlorate (KClO3), aniline (C6H7N), ammo-
nium persulfate ((NH4)2S2O8, APS) were purchased from
Beijing Chemical Factory. All chemicals were analytic grade
and used without any further purification.
2.2. Preparation of graphite oxide
Preparation of graphite oxide is referred to the method of
Wang et al. [30], similar to a process first described in 1898
[31]. In a typical procedure, natural graphite flakes were
added to a mixture of concentrated sulfuric acid and nitric
acid under vigorous stirring. Then potassium chlorate was
added to the mixture slowly over 30 min, with the reaction
flask in an ice bath. The reaction flask was allowed to stir
for 120 h at room temperature. The mixture was washed with
a dilute hydrochloric acid solution (5.2 wt.%) to remove the
sulfate ions, then centrifuged and washed with deionized
water repeatedly until the pH of the supernatant reached 7.
2.3. Preparation of GO/PANI composites
A certain amount of GO was dispersed in 500 ml of deionized
water and the resulting suspension was ultrasonicated under
stirring for 2 h to get a well-dispersed solution. Ten milliliters
of aniline was added to this solution, then the solution was
ultrasonicated for 30 min. One hundred and thirty-six
milliliters of HCl solution (17 wt.%) containing 24 g of the
oxidant (NH4)2S2O8 was slowly added dropwise into the solu-
tion in ice-water bath under vigorous stirring. The dark sus-
pension became green after a few minutes. The reaction
was kept for 4 h. The precipitated product was obtained by
centrifugation at 3500 rpm and washed with ethanol and
deionized water, followed by drying under vacuum at 60 C
for 24 h. The GO/PANI composite sample was labeled as
x%GO/PANI according to the mass ratio x of GO to the com-
posite.
2.4. Characterization
Powder X-ray diffraction (XRD) patterns of the samples were
recorded on an X-ray diffractometer (XRD-6000, Shimadzu,
Japan) with a scanning speed of 5/min from 5 to 60, using
Cu Ka radiation (k = 0.15418 nm) at 40 kV and 200 mA. The
chemical character of the samples was analyzed by X-ray
photoelectron spectroscopy (XPS, ThermoVG ESCALAB 250).
The morphology of the samples was analyzed by transmis-
sion electron microscopy (TEM, Hitachi H-800, Japan).
Fourier-transform infrared spectroscopy (FTIR) measure-
ments were made on a Bruker Vector 22 FTIR spectrometer
using KBr pellets.
3066 CARBON 5 0 ( 2 0 1 2 ) 3 0 6 4 –3 0 7 3
Carrier mobility and carrier concentration were evaluated
by Hall measurement (Keithley 2400; Keithley 2000) using per-
manent magnet system of 0.5 T. The Seebeck coefficient S and
the electrical conductivity r were measured using the 4-probe
method with a Ulvac ZEM-2 equipment in a helium atmo-
sphere. The tested samples for thermoelectric property were
obtained as follows: the composite was compressed into a
cylinder with a diameter of 13 mm and a height of 3–4 mm
under the pressure of 10 ton, and then rubbed with sandpa-
per, finally the specimen was a 3 mm · 3 mm · 12 mm cuboid.
The sample was heated from one end to develop a tempera-
ture gradient along the lateral surface. The temperature dif-
ference between the measurement points was determined
with a thermocouples. The resulting Seebeck voltage was
simultaneously measured across one or both of the like leads
(copper–copper and/or constantan–constantan) of the two
thermocouples. The Seebeck coefficient S was determined
from the slope of the Seebeck voltage versus the temperature
difference through a period of heating and then cooling. The
final result was compensated to remove the contribution to
the Seebeck coefficient S from the leads used to measure
the Seebeck voltage. The electrical conductivity was evalu-
ated from the following equation: r = IL/VA, where A is the
cross section area, L the distance between the electrodes, I
is the current through the sample and V is the voltage be-
tween the two probes. Thermal conductivities of samples
were measured by a Physical Property Measurement System
(PPMS-9T, Quantum Design).
3. Results and discussion
Fig. 1 shows the electrical conductivities of pure PANI and its
composites with different GO contents. The electrical conduc-
tivity increases with the increasing temperature, indicating
that the composite is a semiconductor. Only three tempera-
tures for the investigation were chosen (50, 70 and 90 C), con-
sidering the minimum test temperature of equipment and
unstability of materials at high temperature. The study
mainly focuses on the changes in thermoelectric properties
at different GO contents. The electrical conductivity increases
Fig. 1 – Electrical conductivity of GO/PANI composites with
different GO contents at 50, 70 and 90 C.
with increasing GO content up to 30 wt.%. This behavior can
be explained by the template effect of graphene oxide created
by the exfoliation of GO. With the aid of graphene oxide, the
conductive PANI has a preferably oriented structure, and the
oriented polymer chains allow the carrier to move easily. GO
with higher content can supply more templates for PANI.
When the GO content exceeds a certain value, for example
30 wt.%, a decreased r is observed due to the insulation of
GO. At 90 C, 40%GO/PANI exhibits a slightly higher r than
that of 30%GO/PANI. The negligible increase value in r is with-
in measurement error range, it is not enough large to break
the conclusion that r decreases when GO content exceeds
30 wt.%.
As shown in Fig. 2, the Seebeck coefficient shows great
increase as PANI is filled with GO. The positive Seebeck coef-
ficient indicates that the composite is a P-type semiconduc-
tor. The S of composite is almost constant for different
temperature and GO contents from 10 to 40 wt.%. The maxi-
mum power factor (6.02 · 10 7 W m 1 K 2) is observed in
30%GO/PANI at 90 C (Fig. 3). This value is 2 orders of magni-
tude larger than that of pure PANI (5.34 · 10 9 W m 1 K 2).
As shown in Fig. 4, the thermal conductivity of GO/PANI
composite is basically equivalent to pure PANI. The carrier
mobilities of conductive polymers are much lower than those
of metals because of the amorphous nature of conductive
polymers. For conductive polymers, the charge carrier contri-
bution to the thermal conductivity is generally small while
the phonon contribution is dominant [32]. Numerous inter-
faces in the composites may act as the effective scattering
centers of phonons. Phonons are highly scattered. Thermal
transport in composites is impeded while the electrical con-
ductivity can be maintained by a transport mechanism like
the hopping. This is consistent with the low thermal conduc-
tivity and high electrical conductivity obtained experimen-
tally for GO/PANI composites. Both a constant k and an
increased r contribute to the enhanced thermoelectric perfor-
mance with a maximum ZT of 4.86 · 10 4.
There is a major puzzle in optimizing S, r and k arising from
their interdependence. Efforts to increase the r commonly also
lead to an increased thermal conductivity k. Likewise, the r
Fig. 2 – Seebeck coefficient of GO/PANI composites with
different GO contents at 50, 70 and 90 C.
 CARBON 5 0 ( 20 1 2 ) 3 0 6 4–30 7 3 3067

content increases from 0 to 10 wt.%, the carrier mobility in-

creases greatly. It is also found that the carrier concentration
is almost constant with the increase of GO content. This plays
a major role in the increase of both electrical conductivity and
Seebeck coefficient. As is known, interchain and intrachain
hopping have important effects on the charge carrier transport
in polymers. The carrier mobility is strongly dependent on the
conformation and arrangement of polymer chains. Under the
effect of graphene oxide as a template, the conductive PANI
has a preferably oriented structure. Highly oriented polymer
chains can reduce the barriers of interchain and intrachain
hopping and allow the carrier to move easily because of the
high conjugation. So the carrier mobility increases, resulting
in both increased r and S at the same time. The excess GO
may block the carrier transmission within the PANI chains.
Compared with 30%GO/PANI, the slight decrease in carrier
Fig. 3 – Power factor of GO/PANI composites with different mobility was observed for 40%GO/PANI.
GO contents at 50, 70 and 90 C. Prepared PANI consists of metallic regions with a good
conducting property and amorphous regions with a large
resistance. For GO/PANI composites, metallic regions consid-
ered as ‘‘conductive islands’’ are dispersed in the insulated
area including GO and amorphous regions, as shown in
Fig. 5. The insulated area acts as a barrier to conductivity,
especially at a low temperature because there is less thermal
excitation. Only a few conducting paths are formed in pure
PANI because of the low density of conductive islands. The
introduction of GO results in more metallic regions formed
in PANI due to the preferable alignment of polymer chains.
The formation of more conductive islands in composite
makes carrier transmission more convenient. However, the
excess GO may prevent the PANI chains from ordering their
arrangement. So there is no further improvement in both
electrical conductivity and Seebeck coefficient for 40%GO/
PANI. Carrier transmission in the composite may be illus-
trated as an equivalent circuit shown in Fig. 5. The resistance
Fig. 4 – Thermal conductivity of GO/PANI composites with Ro of conductive island connects with the contact resistance
different GO contents. Rc existing among conductive islands in series to form a
chain-like circuit. Intermittent capacitance Cg, intermittent
resistance Rg and Ro constitute an intermittent circuit. Insu-
tends to increase as the S decreases [33,34]. The approaches lated circuit is made up of the insulated area, it can be re-
that rely on reducing k to enhance ZT were widely adopted garded as an open circuit due to its large resistance Ri.
for the inorganic materials in the past [35]. This paper reports We also measured the thermoelectric properties of the GO/
an effective method to increase r and S at the same time. That PANI blend (Fig. 6), which is prepared by mixing under ultra-
S of the composite do not decrease as its r increases, implying sonic agitation 1 part GO and 9 parts PANI powders polymer-
that the process of adding GO may result in the change in ized without GO. The GO/PANI blend has the lower r and S
either the carrier concentration or the carrier mobility, or both. than those of GO/PANI composite with the same GO content,
The definitive reason can be obtained from the measured car- respectively. This may further verify the template effect of
rier concentration and mobility listed in Table 1. When the GO graphene oxide on PANI. The GO/PANI blend has higher
slightly S than PANI, which could owe to the relatively higher
intrinsic S of GO compared with PANI.
Table 1 – Carrier concentration and carrier mobility of GO/ Recently, Meng et al. [28] indicated that it was the size-
PANI composites with different GO contents. dependent energy-filtering effect caused by the nanostruc-
tured PANI coating layer enwrapped around the CNTs that
Sample Carrier Carrier
contributed to the improvement of thermoelectric properties
concentration mobility
(cm 3) (cm2/V s) for the CNT/PANI composites. This may be an additional expla-
nation for the enhanced thermoelectric performance of the
PANI 1.1 · 1019 0.62 GO/PANI composite in our work, because the PANI coating
10%GO/PANI 1.3 · 1019 2.25
layer formed on the graphene oxide, which could be illustrated
30%GO/PANI 1.5 · 1019 2.56
as Fig. 7. The graphene oxide being electron acceptor and ani-
40%GO/PANI 1.3 · 1019 2.44
line being electron donor form a kind of weak chargetransfer
3068 CARBON 5 0 ( 2 0 1 2 ) 3 0 6 4 –3 0 7 3

Template Effect

Polyaniline Metallic region

Graphene oxide
Amorphous region
carrier transmission

Ro Ro Rg Cg Rg Cg

Rc Rc Ro Ro Ri

Chain-like circuit Intermittent circuit Insulated circuit

Fig. 5 – Conducting analogue schematic of GO/PANI composites.

PANI, as shown in Fig. 8 [37–39]. The strong interactions may

Fig. 6 – Thermoelectric properties of GO/PANI blend at 50, 70
and 90 C.
complex [36]. In GO/PANI composites, PANI deposits orderly on
the surface of the graphene oxide sheet through strong inter-
actions between them. These interactions include electro-
static forces, hydrogen bonding and p–p stacking from the
surface of the graphene oxide and conjugated structure of
induce free anilines to be adsorbed on the surface of graphene
oxide, which as a support template could supply a large num-
ber of active sites for PANI to nucleate. Free anilines are more
competitive to be bound with the surface of graphene oxide
than water molecules. Thus PANI deposited densely on the
surface of graphene oxide [40].
The chain packing of PANI in composite is ordered due to
the template effect of graphene oxide, however it is disor-
dered in the absent of GO. There are some spacing between
molecular chains of PANI. The hopping distance of carriers
is fixed at a certain temperature. Under the guidance of tem-
plate graphene oxide, PANI molecular chains are closely
packed and ordered. The carrier hopping may occur more eas-
ily due to the decreased chain spacing, therefore the carrier
mobility is increased.
Note that some unexfoliated GO remain randomly config-
ured even after ultrasonic treatment, and some gaps may ex-
ist between GO layers to allow the aniline molecules to
wriggle into due to the strong interactions. The growing PANI
polymer chain would wedge away the unexfoliated GO. Then
the unexfoliated GO was broke down into individual graphene
oxide sheet. These strong interactions not only prevent
graphene oxides from aggregating but also promote the uni-
 CARBON
Fig. 7 – Proposed mechanism for GO/PANI synthesis.
hydrogen bonding
electrostatic forces π-π stacking
H H H
N N N NH
+ +
-
- Cl
O n
OH
O
O -
O
OH
Fig. 8 – The diagram of interactions between graphene oxide
and PANI.
form dispersion of graphene oxide sheets with high aspect ra-
tio in the PANI.
FTIR spectra were analyzed to determine the interactions
between PANI matrix and GO sheets. As shown in Fig. 9, three
characteristic peaks of GO at 3429, 1730 and 1058 cm 1, indi-
cating the presence of hydroxyl, carbonyl and epoxy groups,
respectively. For the PANI powder sample, the absorption
peaks located at 1562 and 1481 cm 1 are ascribed to the pres-
ence of quinoid ring and benzenoid rings in the emeraldine
salt, respectively. The C–N stretching of the secondary aro-
matic amine and aromatic C–H bending in the plane are re-
flected in the peaks at 1297 and 1124 cm 1, respectively. The
band at 796 cm 1 indicates the out-of-plane bending vibra-
tions of C–H band in the aromatic ring [41]. In particular,
the peak at 1124 cm 1 is described as ‘‘electronic-like band’’
by MacDiarmid et al. [42]. This is a characteristic peak of con-
ductive PANI and marks the extent of electron delocalization.
The emergence of these peaks above can confirm the success-
5 0 ( 20 1 2 ) 3 0 6 4–30 7 3 3069
Fig. 9 – FTIR spectra of PANI and GO/PANI composites.
ful preparation of PANI under our conditions. Note that the
peak at 1562 cm 1 blueshifted to 1577 cm 1 in GO/PANI com-
posite, which is caused by the withdrawing induction effect of
C=O groups from GO, although there is still conjugative effect
remaining. The carboxyl groups of graphene oxide may be
considered to link with the nitrogen of PANI backbone during
the polymerization [43,44].
The XPS peaks from GO and 30%GO/PANI are shown in
OH
Fig. 10. The C 1s peak region of GO are reasonably decom-
posed into four peaks with binding energies of 287.9 (C=O),
O
287.1 (C–O–C), 285.8 (C–OH) and 284.5 eV (C–C), respectively.
In the case of 30%GO/PANI, the peaks corresponding to C–O–
O
C and C–OH are merged into a new peak situated at
287.2 eV. This is probably due to the increased conjugation
and the change in the C–O–C and C–OH binding energy. The
interactions between the PANI backbone and graphene oxide
sheets result in the increased conjugation and the shift in
binding energy [37]. Remarkably, The C 1s of C=O peak in-
creased to 289.6 eV, implying that the C=O groups of graphene
oxide were doped into PANI. This is consistent with the blue-
shift in C=O groups confirmed by FTIR spectra. The N 1s spec-
tra of the PANI are decomposed into quinonoid imine (–N=),
benzenoid amine (–NH–), and positively charged nitrogens
(N+). As compared with XPS of the PANI, the intensity of the
–N = is decreased and the intensity of N+ is increased in the
30%GO/PANI, indicating that GO doping takes place on the
quinoid segment of the PANI [44].
Powder X-ray diffraction patterns were employed to ana-
lyze GO, PANI, GO/PANI composite and GO/PANI blend
(Fig. 11). For GO specimen, the peak at 2h = 9.6 corresponding
to (0 0 1) reflection peak is observed. It can be calculated that
the interlayer distance of GO is 0.9 nm from the Bragg equa-
tion. The expanded interlayer distance compared with that
of natural graphite (0.335 nm) indicates the existence of hy-
droxyl, carbonyl and epoxy groups on the surface of graphene
sheet. The reflection peak (0 0 1) might depend on the prepara-
tion method and water content in the interlayer of GO. For
PANI specimens, the crystalline peaks appeared at 9.4,
14.8, 20.1, 25.2, 26.5 and 29.8, correspond to (0 0 1), (0 1 1),
3070 CARBON
Fig. 10 – C 1s XPS spectra of GO (a) and 30%GO/PANI (b); N 1s XPS spectra of PANI (c) and 30%GO/PANI (d).
Fig. 11 – XRD patterns of pure PANI, GO, GO/PANI blend and
GO/PANI composites.
(0 2 0), (2 0 0), (1 2 1) and (0 2 2) reflections of PANI in its emeral-
dine salt form, respectively. For the composites, no obvious
GO peaks appear in the XRD pattern, demonstrating that GO
is fully exfoliated into single graphene oxide sheets. It is
found that the full width at half-maximum of the main peaks
at 14.8, 20.1 and 25.2 decreases with the increasing GO con-
tent from 0 to 30 wt.%, corresponding to the more and more
5 0 ( 2 0 1 2 ) 3 0 6 4 –3 0 7 3
ordered PANI chains. It is believed that GO helps to align the
PANI chains and enhances the crystallinity. However, when
the GO content is up to 40%, the peaks become much broader
and weaker than that of 10%GO/PANI or 30%GO/PANI. It indi-
cates that more amorphous regions form in 40%GO/PANI.
This result may be caused by the excess GO acting as ‘‘impu-
rities’’, which hinders the growth of crystallinity and forms
barriers to carrier transport in the PANI chains. This is consis-
tent with the electrical conductivity and carrier mobility ob-
tained experimentally for 40%GO/PANI composite. The
peaks in GO/PANI blend are similar to those of PANI, indicat-
ing that the crystallinity of PANI in the blend doesn’t increase.
GO does not have a template effect on PANI in the preparation
condition of GO/PANI blend.
The nanostructure of the PANI is induced and influenced
greatly by the addition of graphene oxide in the synthesis pro-
cess. The TEM micrographs of pure PANI and GO/PANI com-
posites are shown in Fig. 12. It is apparent that the
composite has different morphology from that of PANI. The
PANI shows granular morphology with 30–40 nm in diameter.
These granules stack together randomly in a disordered state.
The nanoscale patterns of strips are observed from the TEM
images of the composites, confirming that graphene oxide fa-
vors the forming of PANI with ordered molecular structure on
the surface of graphene oxide layer. We infer that anilines are
attached to the surface of graphene oxide firstly and then
form ordered PANI chains during the polymerization. Only a
 CARBON 5 0 ( 20 1 2 ) 3 0 6 4–30 7 3 3071

Fig. 12 – TEM images of PANI (a), 10%GO/PANI (b), 30%GO/PANI (c) and 40%GO/PANI composites (d).

few parts of the graphene oxide are naked. Most parts of the
graphene oxide surface are tightly coated by PANI, implying
strong interactions between graphene oxide and PANI.
We also attempted to reduce graphene oxide into graphene
using hydrazine monohydrate to increase the r of the compos-
ite. However, the result is opposite to our initial expectation.
The conductivity of the 10%GO/PANI composite after reduc-
tion treatment (labeled as 10%GO/PANI-R) is lower than that
of the 10%GO/PANI composite. As is known, HCl-doping and
oxidation levels of PANI are two important factors affecting
the electrical conductivity. During the reduction processes,
the reductant may result in a decrease in both HCl-doping
and oxidation levels of PANI. The concentration of the polaron
in the composite is decreased. Then we treated 10%GO/PANI-R
composite with HCl solution containing (NH4)2S2O8 as an
oxidant to obtain 10%GO/PANI-R-D composite, expecting to
restore the conductive structure. As shown in Fig. 13, reoxida- Fig. 13 – Electrical conductivity of 10%GO/PANI-R and
tion and reprotonation processes restore the conductivity of 10%GO/PANI-R-D composites at 50, 70 and 90 C.
GO/PANI-R composite to a certain extent due to the increased
doping and oxidation levels. But the conductivity is still
inferior to that of the original 10%GO/PANI composite. make the method is a potential route to explore other poly-
This paper firstly reports that GO helps to align the poly- mers, such as polythiophene and polypyrrole.
mer chain and enhances the thermoelectric properties of
the polymer. GO may be a promising candidate component 4. Conclusions
for the further development of lightweight and low-cost poly-
meric composites for thermoelectric applications. Although This paper studied the thermoelectric properties of GO/PANI
the ZT value of GO/PANI composite is smaller than the value composites synthesized by a simple in situ polymerization.
derived for typical inorganic counterpart, the results show the GO was exfoliated into graphene oxide, which as a template
possibility of tuning the thermoelectric properties of the con- to align the PANI chains. PANI with ordered molecular struc-
ductive polymer and open the way for more efficient thermo- ture formed on the surface of graphene oxide. The enhanced
electric devices based on future higher-conductive polymers. thermoelectric properties of PANI mainly stemmed from the
The GO/PANI composite products in the form of powder could increased carrier mobility, which is verified by Hall measure-
be easily processed into various shapes by a simple cold ment. The maximum electrical conductivity and Seebeck
pressing. Simple preparation process and post-processing coefficient reached 751 S m 1 and 28.31 lV K 1, respectively.
3072 CARBON 5 0 ( 2 0 1 2 ) 3 0 6 4 –3 0 7 3
Compared with pure PANI, the almost constant thermal con-
ductivity was observed for GO/PANI composite due to phonon
scattering. The maximum thermoelectric figure of merit ZT
was up to 4.86 · 10 4, 2 orders of magnitude higher than that
of pure PANI. The paper indicated that the lightweight and
low-cost GO/PANI composite may be a promising candidate
for thermoelectric applications.
Acknowledgements
The financial supports from the National Natural Science
Foundation of China (51125010) and Shandong young and
middle-aged scientist foundation (BS2009NY027) are grate-
fully acknowledged.
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