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Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
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Band Engineered P-type RGO-CdS-PANI Ternary Nanocomposites
for Thermoelectric Applications
a a b a
Priyesh V. More* , Chaitanya Hiragond , Abhijit Dey and Pawan K. Khanna *
A ternary hybrid nanocomposite of RGO-CdS-Polyaniline (PANI) is prepared by a simple two staged in-situ method for its
thermoelectric studies. For this purpose, CdS quantum dots were first prepared with varying concentrations in the

www.rsc.org/
presence of reduced graphene oxide to form RGO-CdS nanocomposites using 3-mercaptopropionic acid as a linker.
Polyaniline was then prepared in-situ in presence of RGO-CdS nanocomposites to eventually obtain RGO-CdS-PANI
nanocomposites. The electrical conductivity, seebeck coefficient and power factor of the RGO-CdS-PANI nanocomposites
were calculated with various loading of RGO-CdS nanocomposite in PANI. The final RGO-CdS-PANI nanocomposites
delivered high electric conductivity in the order of 105 S/m and showed strong re-dispersion in DMF and ethanol. The
effective band alignment and decreased thermal conductivity in RGO-CdS-PANI nanocomposite resulted in p-type
behaviour and high power factor value.

Introduction
Nanomaterials possess unique chemical, physical, and
mechanical properties thus, find their application for a wide
variety of devices like photovoltaics, Transistors, LEDs, sensors
etc. [1-2]. Similarly, nanomaterials showing thermoelectric (TE)
properties have attracted growing attention due to direct
conversion between thermal energy to electrical energy [3–4].
The Thermoelectric devices have been recognized for reducing
global energy consumption, a long time solution and highly
promising transformative technology. These energy utilizations
are ecofriendly and non-polluting thus, such devices attract
great attention by the global research and industrial
communities [5-8]. However, the relatively high cost and poor
processability of inorganic semiconductor TE materials are
impeding their applications to advanced thermoelectric
systems [9]. The efficiency of thermoelectric materials and
devices are characterized by the dimensionless figure of merit
(ZT), which contains three physical quantities i.e. Seebeck
coefficient (S) electrical conductivity (ϭ) and thermal
conductivity (k). The figure of merit can be expressed by the
2
equation ZT = (S σ/κ) T, where T is the absolute temperature
[10-11]. These parameters are correlated with each other and
are relatively difficult to optimize at once. Nowadays, in field
of materials technology, combining various materials through
synergy is one of the most successful approaches to achieve
specific goals with great efficiency in properties and cost
effectiveness. [12-15]. In this respect, graphene and its
composites are one of the class of materials which have great
applications in the various field including thermoelectrics. Due
to the incredible properties of graphene, along with their
relatively low cost, facile processing and recyclability, it can be
utilized in various advanced applications [16]. Graphene has
zero band gap, high electrical conductivity and mixing it with
semiconducting nanomaterials results in inter-material charge
transfer. Thus, when graphene combines with nanomaterials
like, PbSe, PbTe, CoSb3, etc. the electrical conductivity of the
resultant composite increases significanty [17].
The nanocomposites of conducting polymers with
inorganic material like graphene are also a topic of interest
among researchers because of resultant low thermal
conductivity and high electrical conductivity [18-19]. The
addition of conducting polymer imparts easy processing for
the composite and reduces thermal conductivity while
graphene improves the electrical conductivity [20-21]. The
conducting polymers such as polyaniline (PANI),
polythiophene, PEDOT−PSS, polyacetylene, polypyrrole, and
their derivatives have a great potential for use in
thermoelectric energy applications [22-25]. The conducting
polymers posses unique features like high mechanical
flexibility light weight, low-cost synthesis, solution
processability, and printability which can be highly
advantageous for thermoelectric applications [26-30].
However, it is observed that the use of conducting polymers

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along with graphene/CNT failed to deliver high thermolectric
power factors. Also, the processing of these composites is
difficult due to their low re-dispersion in solvents.
Thus, in the present work, we have typically combined RGO
with CdS QDs and PANI to enhance the thermoelectric
properties and improve the re-dispersion. For this purpose,
we first performed the in-situ synthesis of RGO-CdS
nanocomposites with three different ratios of RGO to CdS.
These RGO-CdS nanocomposites were thoroughly
characterized and then combined with polyaniline by
polymerizing aniline in-situ in their presence to form ternary
RGO-CdS-PANI nanocomposites. The as-formed RGO-CdS-PANI
nanocomposites with varied concentration of RGO-CdS
nanocomposites were then used for thermoelectric studies by
forming a thick pellet. The measurement of Seebeck
coefficient, thermal conductivity, electrical conductivity was
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performed experimentally and Power factor (PF) was
calculated from these values. The effect of variation in CdS
concentration on thermoelectric properties of RGO-CdS-PANI
nanocomposite was studied in detail.
Experimental
Chemicals and methods:
All chemicals and solvents were purchased commercially.
Cadmium chloride (CdCl2), Sodium sulphide (Na2S) and other
solvents were obtained from Sigma Aldrich India Ltd. All
chemicals and solvents were reagent or analytical grade and
were used as received. Graphitic flakes (Reinstenano ventures)
and aniline (Merck, India) were also purchased commercially.
UV-Visible spectra were recorded in toluene at room
temperature using SPECORD 210 PLUS (analytikjena, Germany)
UV spectrophotometer. Photoluminescence (PL)
measurements of solutions were measured using Cary Eclipse
Fluorescence Spectrophotometer G9800A of (Agilent
Technologies, USA). The samples were excited at 350 nm and
emissions were monitored between 370-800 nm. Powder X-
ray diffraction patterns were measured using Cu-Kα
(λ=1.5406Å) radiation on Mini Flex Rigaku X-ray
diffractometer.
Scheme 1: Schematic representation of RGO-CdS-PANI preparation nanocomposites for thermoelectric applications.
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SEM images and elemental analysis were performed on Carl
Zeiss Scanning electron microscope. Infrared (FTIR) spectra
were recorded at room temperature from 4000 cm-1 to 400
cm-1 with FTIR Perkin Elmer spectrum two (USA). TEM images
were obtained from FEI-TECNAI G2 (Czech Republic).
Sustainable Energy & Fuels Accepted Manuscript
Synthesis of RGO-CdS nanocomposites
Graphene was prepared in three steps as reported in the
literature [31]. In the first step, graphite oxide was prepared
from graphitic flakes by the Hummers method. In the second
step, thermally expanded graphene oxide (TEGO) was
prepared by thermal expansion/exfoliation at 1050 °C (Ar, 30
s). Finally, RGO was obtained by the hydrogen reduction of
TEGO at 400 °C for 2h. In the second stage, we adopted the in-
situ synthesis method to prepare RGO-CdS nanocomposite
where RGO nanoplatelets were first re-dispersed in DMF. CdS
was then grown in this solution by using 2-mercaptopropionic
acid as a capping agent and sodium sulphide as sulphur source.
We varied the ratio of RGO to CdS (wt/wt %) as 1:0.1 (G2),
1:0.25 (G3) and 1:0.5 (G4) by varying the concentration of
cadmium and sulphur sources during the synthesis.
Synthesis of RGO-CdS-PANI nanocomposite for
thermoelectric applications
In the last stage, the as-prepared RGO-CdS nanocomposites
with varied concentrations (G1, G2 and G3) were dispersed in
HCL solution separately and polyaniline was grown in-situ by
polymerisation of aniline using ammonium sulphate as an
oxidizing agent. The final RGO-CdS-PANI nanocomposite
samples with various loading and ratios were subjected to cold
pressing to form thick pellets for further testing for
thermoelectric properties. The overall synthesis process of
formation of RGO-CdS-PANI nanocomposite is mentioned in
Scheme 1. The loading of as-prepared RGO-CdS
nanocomposite in PANI was varied from 0.1 to 0.4 wt% to
observe its influence on thermoelectric properties. The as-
prepared RGO-CdS nanocomposite was thoroughly
characterized to know the degree of CdS formation on RGO
nanoplatelets.
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(~3.35 eV) was much higher than the bulk band gap of CdS
a. (~2.2 eV). The observed absorption profiles of G2, G3 and G4
samples were typically similar to the absorption profile of CdS
QDs. Since, RGO is not expected to show any absorbance in
Absorbance

the visible region the only absorption possible for these

RGO/CdS/PANI
samples was due to the presence of CdS QDs in the
nanocomposites. Thus, the presence of CdS QDs was
CdS confirmed in as-prepared G2, G3 and G4 nanocomposites.
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G2 However, in case of RGO-CdS-PANI nanocomposite with 0.4

G3 wt% loading of G4 sample, two broad peaks covering the
G4
entire long-UV and visible region of the spectrum were
300 400 500 600 700 observed. These broad peaks were signature peaks for
Wavelength(nm) emeraldine base polyaniline confirming the formation of
polyaniline in the RGO-CdS-PANI nanocomposite. In addition
b. Ex@350 nm
to UV-visible spectroscopy, we also performed
photoluminescence (PL) spectroscopy for the as-prepared CdS
PL Intensity(a.u.)

QDs, G2, G3 and G4 and RGO-CdS-PANI nanocomposites. The

emission profile of CdS QDs showed a typical broad peak
CdS centred at 525 nm which is due to the surface related defects
RGO/CdS/PANI
created by the thiol group of MPA. However, the PL spectra of
G4 all the G2, G3 and G4 nanocomposites samples showed a
G3 featureless profile with little or no photoluminescence. Similar
G2 PL profile featuring quenching of photoluminescence was
400 500 600 observed for RGO-CdS-PANI nanocomposite with 0.4 wt%
Wavelength(nm) loading of G4 sample. This observation was found highly
satisfying as complete quenching of PL peak highlights the
c. #RGO
*CdS effective charge transfer between CdS QDs, RGO sheets and
#(002)
PANI. The excited electrons are expected to trap in the surface
*(111) #(101)
/ #(100) #(004) related effects created by the MPA capping ligand and the
Intensity (a.u.)

G4 holes are expected to enter the Fermi level of RGO. Such

10 20 30 40
2θ
Figure 1: a) UV-Visible, b) PL spectra and c) XRD of RGO-CdS
nanocomposites with different concentrations of CdS QDs.
Results and Discussion
The presence of RGO and CdS QDs in the RGO-CdS
nanocomposite was confirmed by UV-visible and PL
spectroscopy (Figure 1a and b). For this purpose, we
separately synthesized CdS QDs alone by the similar method
using MPA as capping agent. The UV-visible spectrum of CdS
alone (See Figure SI 1) showed absorption peak at 370 nm
confirming the formation of CdS QDs as the obtained band gap
efficient transfer of charges from CdS to RGO makes the as-
G3 prepared nanocompistes a highly promising candidate for
electronic applications.
G2 The XRD studies of all the RGO-CdS samples showed a
sharp characteristic peaks corresponding to (002), (100), (101),
50 60 70 80 90
(004), (103) and (110) crystal planes of graphite (Figure 1c).
(degrees) The dominance of graphitic peaks was expected due to the
high crystalline nature of the stacked RGO sheets. The CdS QDs
when synthesized alone showed broad peak profile
highlighting its small size and amorphous nature (Figure SI. 1).
The broad peak of CdS QDs was evident in G4 sample where
the ratio of RGO: CdS was 1:0.5 (w/w%). It was obvious that
broad peak profile of CdS QDs was evident in the G4 sample
due to the high concentration of CdS QDs present in this
sample. The broad peak was obtained from 20 to 35° for this
sample highlights the merging of peaks (111) and (220) of
cubic CdS crystal planes. For further confirming the presence
of CdS QDs in the nanocomposites, we performed Raman
spectroscopy of samples

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a Dominated by PANI
doubly degenerate E2 branches (Raman active only) [32]. In
the present study, we observed six broad optical vibrational
RGO/CdS/PANI
Raman peaks between approximately 290-480, 750-1000,
−1
1100-1380, 1600-1850, 2000-2200 and 2500-2700 cm in G2,
Intensity(a.u.)
G4
G3 and G4 samples as shown in Figures 2a.The peaks obtained

Sustainable Energy & Fuels Accepted Manuscript

are broad in nature and hence reflecting the presence of high
G3 density of photons in the nanocomposites. The presence of E-
modes represents high phonon scattering in the sample which
G2 may reduce the thermal conductivity in the present
1LO 3LO D G+D' G' nanocomposite system. The RGO-CdS-PANI nanocomposite
500 1000 1500 2000 2500 3000 with 0.4 wt% loading of G4 samples showed domination of
Wavenumber(cm-1) PANI in the nanocomposite. The ν(CC) band at c.a. 1600 cm-1,
the imine ⱱ(C=N) and δ(NH) vibration band near 1500 cm-1, the
b RGO/CdS/PANI
semibenzenoid polaronic ⱱ (C~N+•) band at 1350 cm-1, and the
band of C-H in plane bending vibration around 1200 cm-1
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. representing PANI were observed.

The prime objective of preparing such nanocomposites was
Intensity(a.u.)

2864, -CH2
2929, -CH2
3442,-OH 1666, O-H 1566, C=C 671, CdS
4000 3000 2000
Wavenumber(cm-1)
Figure 2: a) FTIR, b) Raman of as-prepared nanocomposites
confirming the presence of CdS, RGO, PANI and MPA.
In bulk CdS crystals, the rule for selection of Raman scattering
is q ≈ 0, where q is the wave vector. However, in CdS QDs, the
selection rule (q ≈ 0) is relaxed due to the interference of
lattice periodicity. The group theory predicts seven optical
active branches at the zone centre in CdS crystal structure.
These optical branches can be classified as symmetric A1 and
doubly degenerate E1, both active in Raman and infrared, two
G4
to create a linkage between CdS and RGO surfaces which may
G3 hold the CdS QDs over RGO sheets. MPA may play a role in
such linkage as it has two functional groups in its structure
G2 (thiol and carboxylic groups) resulting in uniform coverage of
CdS QDs over RGO. The thiol group is known to be form a
1142,C-O
strong bond with surface Cd atoms on CdS QDs and we assume
that the carboxylic group may attach to the RGO surface to
1000
deliver such linkage. The FTIR spectra confirmed the presence
of MPA in all the samples (Figure 2a). The relative peaks for
carboxylic acids i.e. 1720 cm-1 and two peaks between 1210-
1320 cm-1 resembling C=O and C-O stretching were also
clearly observed for all the samples. The peak for S-H from
thiol (2500 - 2600 cm-1) was absent in all the samples
confirming the bond between S atom from thiol and Cd from
CdS QDs. The FESEM images showed in Figure 3 (a-c) of the
RGO-CdS nanocomposite confirmed the uniform coverage of
CdS quantum dots over RGO as the ratio of CdS was increased
from G2 to G4. The coverage of CdS QDs over RGO sheets was
found to be high in the G4 sample as uniform calculated from
the acquired image.

Figure 3: a, b & c) FESEM images of RGO-CdS nanocomposite with different ratios of CdS and RGO, d) TEM images of G4 sample
with scale bar 100 nm e) TEM images of G4 sample with scale bar 10 nm and 2 nm for inset, and f) schematic representation
showing MPA linkage between graphene sheet and CdS QDs.

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a. G2/PANI
b.

Electrical conductivity (S/m)

G3/PANI
G4/PANI
100k

Sustainable Energy & Fuels Accepted Manuscript

10k

1k

0.1 0.2 0.3 0.4

Filler concentration (wt.%)
35
c. 100
G2/PANI d.
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G2/PANI
G3/PANI
Seebeck Coefficient (µV K)

G3/PANI

Power Factor (µW m K )

G4/PANI 80 G4/PANI

2
30

-1
60

25
40

20 20

0
15
0.1 0.2 0.3 0.4 0.1 0.2 0.3 0.4
Filler concentration(wt.%) Filler concentration(wt.%)

e.

Figure 4: a) SEM image of RGO-CdS-PANI nanocomposite with 0.4 wt% loading of G4 sample plus photograph of its re-dispersion in ethanol
(inset), Plots of b) Electrical conductivity, c) Seebeck coefficient, d) Power Factor versus filler concentration and e) Graphical representation
for energy levels of RGO-CdS-PANI nanocomposite promoting p–type charge transport and energy filtering edffect.

presence of CdS QDs was observed on RGO sheets. The EDX
analysis confirmed the increase of elemental Cd and S from G2
to G4 samples (Figure S4). The HRTEM images of G4 sample
further confirmed the presence of CdS QDs on RGO sheets and
also the exfoliation of RGO sheets (See Figure 3). It was
observed that small aggregates of CdS QDs were uniformly
decorated over plane of CdS was wrecked RGO nanosheets.
The lattice fringes were clearly visible and the lattice Spacing
of d=0.205 nm for (220) crystal plane. The SEM and TEM
images of RGO-CdS-PANI nanocomposite with 0.4
wt% loading of G4 samples visibly showed the presence of
globular PANI aggregates along with CdS coated RGO sheets in
the sample (Figure 4a). The lattice fringes of CdS QDs were
clearly visible in the TEM images which confirmed its existence
over RGO sheets in it (Figure SI. 5).
Thermoelectric application of RGO-CdS in polyaniline matrix:
The Electrical conductivity, Seebeck coefficient/thermopower
and power factor are the three main components which
describes thermoelectric properties. The measurement of
electrical conductivity and thermopower was carried out

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experimentally at room temperature (RT) and at ambient
2
obtained values of S and σ (PF=S σ). Interestingly, we
observed that the electrical conductivity of RGO-CdS-PANI
nanocomposites increased with the increase in the filler (G2,
G3 & G4) concentration (Figure 4b). The rise in electrical
conductivity was mainly due to addition of RGO-CdS
nanocomposites, as pristine PANI showed low electrical
-4
conductivity in the range of 10 S/m. The Seebeck coefficient
also exhibited an interesting trend as maximum value was
obtained for a sample with 0.2 wt.% of G4 loading while lowest
value was obtained for a sample with 0.4 wt.% of G4 loading
(See Figure 4c). The PF of the RGO-CdS-PANI nanocomposites
increased as the filler concentration increased and reached a
-1 -2
very high value (91.95 µW m K ) for 0.4 wt.% loading of G4
(Figure 4d). This PF value was found slightly less than the
highest ever reported for PANI based system. Recently, Wang
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-1 -2
et.al reported a PF of 101 µW m K using a composite of
43
PANI, SWNT’s and Te nanorods . The present nanocomposite
system however, can be more advantageous as a low thermal
conductivity (0.14 for 0.4 wt% G4 loading) was obtained as
compared to 0.3 for the above reported material. The low
thermal conductivity and high electrical conductivity of the
present RGO-CdS-PANI nanocomposite (with 0.4 wt% loading
G4) yielded a excellent ZT value of 1.97.
The electrical conductivity in the present nanocomposite
system may have followed the percolation law which helps to
predict an increase in electrical conductivity till it reaches to a
critical concentration level of the filler. Generally, when two
different materials with a large difference in electrical
conductivities are mixed, such phenomenon is observed.
Interestingly, the role of CdS QDs was vital in obtaining high PF
values. It should be noted that the concentration of RGO and
PANI was kept constant in RGO-CdS and RGO-CdS-PANI
nanocomposites respectively. Thus, only the CdS QDs
concentration was systematically increased in the final RGO-
CdS-PANI nanocomposites as the loading of G2, G3 and G4 was
increased. The PF value of RGO-CdS-PANI nanocomposite with
0.4 wt.% G3 loading was ~75 while with similar G4 loading was
~92 (Figure 4d). Thus, the increase in CdS QDs concentration
(0.25 to 0.5 wt% with respect to RGO) in the as-prepared RGO-
CdS-PANI nanocomposites played a vital role in increasing the
PF value. Additionally, the increase in CdS QDs concentrations
(from G2 to G4) also leads to the increase in electrical
conductivities of the nanocomposites i.e. samples with G4
loading has the highest values followed by G3 then G2.
Mechanism and role of various interfaces in charge transport:
The most peculiar part of thermoelectric properties is the
interdependency of electrical conductivity, Seebeck
coefficient, and thermal conductivity. The electrical and
thermal conductivity of the thermoelectric material enhances
and reduces simultaneously. RGO possess high electrical and
thermal conductivity hence; it is not an ideal candidate for
thermoelectric applications. In the present case, the
decoration with CdS QDs over RGO and PANI matrix helps to
decouple electrical and thermal conductivity in the as-
prepared nanocomposites. Since, the thermal conductivities of
both CdS and PANI are more than 10 times lower than that of
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conditions. The Power factor (PF) was calculated from the
graphene, the present nanocomposites may offer high
electrical conductivity but low thermal conductivity. The
broadness of the RAMAN peaks of these nanocomposites
hinted high scattering of phonons which may lower the
thermal conductivity.
Sustainable Energy & Fuels Accepted Manuscript
In present study, CdS QDs were prepared over and in
between the RGO layers during processing. As a result, the
tendency of graphitic stacking in the as-prepared
nanocomposite may have reduced. The decoration of CdS QDs
obstructs the phonon transport but permits charge transport
which further results in decrease of thermal conductivity. The
FESEM images revealed a uniform presence of RGO in all the
samples creating a good network of exfoliated RGO sheets.
The uniformly distributed RGO increases the interfacial area
which facilitates high charge mobility and high carrier transfer
between PANI-RGO and CdS-PANI interfaces. However, it has
been reported previously that a thiol based capping ligand may
form an electron trapping centre by creating an energy level
44
near the valence band of CdS QDs . Such electron trapping
centre can be formed due to MPA capping ligand blocking the
electron transport from CdS QDs to RGO. Further, the
conduction band of CdS QDs is assumed to be below the
LUMO of PANI while the valence band of PANI is situated
above the valence band of CdS QDs. The band alignment in the
present nanocomposites favours the electron transfer from
PANI to CdS QDs and hole transfer from CdS QDs to PANI after
thermal or visible light excitation. Such charge transfer will
increase the electron and hole density in CdS QDs (conduction
band) and PANI (HOMO) respectively. Since, the MPA ligand
binds the CdS and RGO together; the excited electrons will not
transfer from CdS to RGO due to their difference in energy
levels. However, the energy level of RGO is expected to be
above the HOMO of PANI which will favour the hole transfer
from PANI to RGO (Figure 4a). Hence, the as-prepared RGO-
CdS-PANI nanocomposite behaves like a p-type material which
45
was evident from the positive seebeck coefficient values .
Furthermore, the work function of PANI (emeraldine base) is
known to be near 5 eV while the work function of CdS and
46
RGO is ~3.9 and 4.7 eV repectively . We assume that a small
energy barrier may be present at the PANI/ RGO interface. It
has been reported that the inorganic/organic hybrid
nanocomposites exhibit an energy filtering effect where the
carriers possessing high energy jump the energy barrier at the
interface. The low energy carriers are not allowed to pass
through the interface and thus, leading to enhancement of low
47
electrical conductivity and high Seebeck coefficient . In the
present ternary nanocomposites, two different interfaces
(PANI-RGO, and PANI-CdS) are active for passage of charge
carriers. The obvious enhancement in the Seebeck coefficient
for the low concentrations of G2, G3 and G4 in RGO-CdS-PANI
nanocomposites films may be attributed to the synergetic
energy filtering effect at these two interfaces of PANI-RGO and
CdS-PANI. However, when the concentration of G2, G3 and G4
was increased in the RGO-CdS-PANI nanocomposite, the
Seebeck coefficient decreased. The decreased Seebeck
coefficient could be a result of increase in population of high
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Table 1: Compilation of recent reports on thermoelectric properties of PANI based composite materials

PANI based composites for Thermoelectric σ, S/m S, µV/k κ, W/mK Calculated PF (S2σ),
studies µW m-1K2
PANi + SWCNT composites with different SWCNT 10-125 (RT) 11-40 0.5-1 0.5-5 (300K)

Sustainable Energy & Fuels Accepted Manuscript

34
(RT) (RT)
35 4
PANi + unoxidized SWCNT 5.30×10 33 -- 0.6
PANi + HCL+ MWCNT (40%) 36 1.71×103 10 -- 0.17

PANI + CNT (15.8%) 37 6.1×103 29 0.4-0.5 5

38
PANi + HCL +Graphene (50%) 123 34 3.3 14
PANi + GNP (In situ polymerization with ZT (300K) =
-6
protonation ratio- 0.2) 150 7 0.6 3.68×10
4 -6
Neat PANi 2×10 5 74 3.04×10
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-4
Neat GNP 5900 33 13 1.51×10
4 -4
PANI/GNP (50mM, as made) 1.74×10 19 15 1.26×10
PANI/GNP (50mM, reprotonated) 39
40 3 -3
PANI + 30% Graphene (In-situ polymerization) 5×10 at 12 -- ZT= 1.95 × 10 at 453 K
323K
PANI at 420K 500 13 -- 0.1
PANI + 5-30% Graphene 41 700-4.0×103 28-32 -- 0.4-2.6
42 4
PANI + HClO4+ Graphite (50 wt.%) 1.2×10 19 1.2 1.2
43 2
PANI/SWNT/Te nanorods 3.45x10 54 0.3 101
Present work
PANI + 0.4 wt.% RGO-CdS
G2 3.6×103 20 0.58 1.6 (ZT= 8.4x10-3)
G3 1.7×105 21 0.27 ~75 (ZT= 0.833)
G4 2.9×105 18 0.14 ~92 (ZT = 1.97)

energy charge carriers resulting in higher electrical
conductivity. The RGO-CdS-PANI nanocomposites represent a
brilliant description in which temperature gradients have been
maintained between two edges of the material resulting in
generation of electric potential. The schematic representation
of the charge transport and the energy filtering effect in the
present RGO-CdS-PANI nanocomposite is shown in Figure 4e.
Overall, such favourable network of the as-prepared RGO-CdS-
PANI nanocomposite may promote high electrical conductivity
but reduce the thermal conductivity.
To justify the claims of the present work, a summary of the
latest thermoelectric reports based on PANI matrix has been
highlighted in Table 1. The as-synthesized RGO-CdS-PANI
nanocomposites showed strong re-dispersion in common
solvents such as DMF and ethanol which was stable for more
than 08 weeks (Fig SI.2). We believe that the strong re-
dispersion could be due to the high exfoliation of RGO
resulting in small sub-micron sized RGO-CdS nancomposites
(Fig SI.3.). These small sized RGO-CdS sheets along with
globules of PANI could easily disperse in the solvent medium.
The high re-dispersibility of these nanocomposites may be
significant for their application in flexible thermoelectric
devices where solution processed or printed devices are
fabricated. Additionally, the high electrical conductivities (in
5
order of 10 S/m) and suitable energy band positioning can be
vital for utilizing these nanocomposites for various energy and
electronic applications.
Conclusion
A highly effective ternary hybrid thermoelectric material in the
form of RGO-CdS-PANI was prepared by first varying the
concentration of CdS QDs with respect to RGO and secondly
RGO-CdS nanocomposites with respect to PANI. The
characterization techniques revealed the uniform coverage of
CdS QDs on RGO sheets as MPA facilitated a linkage between
RGO and CdS QDs. The Raman analysis of the nanocomposites
hinted a high phonon scattering supporting the low thermal
conductivity. The band alignment between RGO, CdS QDs and
PANI promoted p-type electrical conductivity and
demonstrated a synergetic energy effect for charge transport.
We observed that the increase in concentration of CdS QDs
and RGO in the final RGO-CdS-PANI nanocomposites resulted
in enhanced electrical conductivity and thermopower (power
factor). The role of MPA capped CdS QDs was vital in
facilitating the hole transport (and prohibiting the electron
transport) to impart p-type behaviour in the nanocomposites.
The obtained power factor values (at R.T.) for 0.4 wt% loading

This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 7

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 Please do notEnergy
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ARTICLE
of RGO-CdS nanocomposite in PANI matrix are one of the
highest reported for PANI based TE materials. The present
RGO-CdS-PANI nanocomposites can be considered a highly
suitable material for flexible thermoelectric devices or fabrics
due to its high re-dispersion and easy processing.
Acknowledgement:
We thank Vice Chancellor (DIAT) for support. PM thanks DST,
Govt. of India for research grant through DST INSPIRE AWARD
project No. IFA-13-PH-68.
Notes and references
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DOI: 10.1039/C7SE00290D

Band Engineered P-type RGO-CdS-PANI Ternary

Nanocomposites for Thermoelectric Applications
Priyesh V. Morea*, Abhijit Deyb, Chaitanya Hiragonda and P. K. Khannaa*

Sustainable Energy & Fuels Accepted Manuscript

TOC
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The presence of CdS QDs enhances the electrical conductivity and power factor but
considerably lowers the thermal conductivity of the nanocomposite. The present RGO/CdS
QDs/PANI nanocomposite restricts phonons but permits electrical charges making it
thermally disconnected but electrically connected material for efficient thermoelectric
applications.